地质聚合物原料组合物、地质聚合物前驱浆液及应用和高温固井的方法

Abstract

本发明涉及地质聚合物领域，公开了一种地质聚合物原料组合物、地质聚合物前驱浆液及应用和高温固井的方法。地质聚合物原料组合物包括：硅铝质原料、表面改性剂、激活剂、分散剂、助溶剂、增强剂和消泡剂；所述表面改性剂为酞酸酯偶联剂。利用该组合物可制备成具有延迟固化性能的地质聚合物前驱浆液，在60‑100℃条件下的固化时间大于120min，流动度大于18cm，固化1天后地质聚合物的抗压强度大于7MPa，固化3天后地质聚合物的抗压强度大于14MPa。可实现在油气井地下高温条件下延长地质聚合物前驱浆料的固化时间，满足固井施工的要求。

Description

Technical Field

[0001] This invention relates to the field of geopolymers, and more particularly to a geopolymer raw material composition, a geopolymer precursor slurry, its application, and a method for high-temperature cementing. Background Technology

[0002] Geopolymers are active silicon-aluminum oxide materials that, under the action of an alkaline activator, have their Si-O and Al-O bonds opened and condensed into [SiO4] groups. ]4- and [AlO4] 5- Geopolymers are three-dimensional network structures composed of structural units, forming aluminosilicate polymers. Geopolymers are particularly suitable for cementing various complex oil and gas wells. Compared to oil well cement, geopolymer materials have significant advantages in high-temperature stability, corrosion resistance, durability, and energy conservation and emission reduction during production, showing promise as a replacement for traditional oil well cement. However, the excessively rapid hydration rate during the preparation of geopolymers is the biggest obstacle to their application, especially in the high-temperature downhole environment where the solidification process is difficult to control.

[0003] CN101323778A discloses a metakaolin-slag-based polymer for oilfield cementing and its high-temperature retarder. The high-temperature retarder comprises 80-90% alkaline earth metal salt and 10-20% inorganic sulfate; wherein the alkaline earth metal salt is one or a combination of magnesium chloride, calcium chloride, barium chloride, calcium nitrate, and barium nitrate. This high-temperature retarder can control the setting rate of the metakaolin-slag-based polymer for oilfield cementing under high-temperature conditions and regulate key properties such as curing time and strength.

[0004] CN108947298A discloses a geopolymer-reinforcing retarder. This geopolymer-reinforcing retarder is an aqueous solution composed of one or more of a carbohydrate compound and a sugar alcohol compound, wherein the percentage of carbohydrate compound is 0-80%, sugar alcohol compound is 0-80%, and water is 10-90%. This retarder can prolong the setting time of the geopolymer, improve its workability, and enhance its compressive strength.

[0005] The above methods all control the solidification process of geopolymer precursor slurry by adding additives other than those in the geopolymer system, without involving any improvement to the raw materials used to prepare the geopolymer. Summary of the Invention

[0006] This invention addresses the problem of rapid hydration of raw materials during the preparation of geopolymers, especially the excessively rapid solidification and difficulty in controlling the precursor slurry under high-temperature downhole environments. It provides a geopolymer raw material composition, a geopolymer precursor slurry, its application, and a method for high-temperature cementing.

[0007] To achieve the above objectives, a first aspect of the present invention provides a geopolymer raw material composition comprising: a silica-alumina raw material, a surface modifier, an activator, a dispersant, a cosolvent, a reinforcing agent, and a defoamer; relative to 100 parts by weight of the silica-alumina raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, and the defoamer is 0.1-1 parts by weight;

[0008] The surface modifier is a phthalate coupling agent.

[0009] A second aspect of the present invention provides a geopolymer precursor slurry, which comprises: water, modified silica-alumina raw material, activator, dispersant, cosolvent, reinforcing agent and defoamer;

[0010] The modified aluminosilicate raw material is obtained by modifying the aluminosilicate raw material with a surface modifier; the surface modifier is a phthalate coupling agent.

[0011] Relative to 100 parts by weight of the aluminosilicate raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, the defoamer is 0.1-1 parts by weight, and the water is 50-100 parts by weight.

[0012] The third aspect of this invention provides the application of the geopolymer precursor slurry described in the second aspect above in high-temperature cementing.

[0013] A fourth aspect of the present invention provides a method for high-temperature cementing, wherein the method includes: injecting the geopolymer precursor slurry described in the second aspect below into the well, obtaining a geopolymer after solidification, and using the geopolymer for cementing;

[0014] Curing conditions include: temperature of 60-100℃ and pressure of 21-60MPa.

[0015] Through the above technical solution, the geopolymer raw material composition provided by this invention can be used to prepare a delayed-curing geopolymer precursor slurry, which is further cured to obtain the geopolymer. The geopolymer precursor slurry has a curing time greater than 120 min at 60-100℃, a fluidity greater than 18 cm, a compressive strength greater than 7 MPa after 1 day of curing, and a compressive strength greater than 14 MPa after 3 days of curing. This allows for extending the curing time of the geopolymer precursor slurry under high-temperature underground conditions in oil and gas wells, meeting the requirements of well cementing operations and demonstrating broad application prospects. Detailed Implementation

[0016] 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.

[0017] The first aspect of the present invention provides a geopolymer raw material composition comprising: a silica-alumina raw material, a surface modifier, an activator, a dispersant, a cosolvent, a reinforcing agent, and a defoamer; relative to 100 parts by weight of the silica-alumina raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, and the defoamer is 0.1-1 parts by weight; wherein the surface modifier is a phthalate coupling agent.

[0018] The geopolymer raw material composition provided by this invention contains a specific surface modifier that can be used together with aluminosilicate raw materials to form modified aluminosilicate raw materials. Based on this, it can cooperate with other components in the composition to achieve a synergistic effect, thereby obtaining a delayed-curing geopolymer precursor slurry and geopolymer after treatment.

[0019] According to the present invention, the components in the geopolymer raw material composition, based on satisfying the above-mentioned quantitative relationships, preferably, relative to 100 parts by weight of the aluminosilicate raw material, are: 4-6 parts by weight of the surface modifier, 30-60 parts by weight of the activator, 0.4-0.6 parts by weight of the dispersant, 8-15 parts by weight of the cosolvent, 2-3 parts by weight of the reinforcing agent, and 0.4-0.6 parts by weight of the defoamer.

[0020] According to the present invention, the phthalate coupling agent can perform surface modification on the aluminosilicate raw material, improve the hydrophobicity of the aluminosilicate raw material, reduce the number of surface functional groups, and thereby reduce the alkali solubility rate of the aluminosilicate raw material.

[0021] In this invention, the phthalate coupling agent is selected from at least one of pyrophosphate-type monoalkoxy titanate, bis(dioctyloxypyrophosphate) ethylene titanate and isopropyltris(dodecylbenzenesulfonyl) titanate, preferably pyrophosphate-type monoalkoxy titanate.

[0022] According to the present invention, the aluminosilicate raw material can be any conventional active aluminosilicate oxide material used in the preparation of geopolymers. Preferably, the aluminosilicate raw material is selected from at least one of calcined kaolin, fly ash, and blast furnace slag, and more preferably calcined kaolin.

[0023] According to the present invention, as the particle size of the aluminosilicate raw material decreases, its specific surface area increases, and its reactivity increases. Upon contact with an alkaline activator, the Si-O and Al-O bonds dissociate more rapidly. For the purpose of controlling the reactivity of the aluminosilicate raw material, preferably, the average particle size of the aluminosilicate raw material is 200-325 mesh.

[0024] According to the present invention, the calcined kaolin is obtained by calcining kaolin ore at high temperature. The activity of the obtained calcined kaolin can be effectively controlled by controlling the calcination temperature of the kaolin ore. Generally, kaolin ore exhibits activity after calcination at 600-850℃, with the strongest activity after calcination at 700-750℃. For the purpose of controlling the reactivity of the calcined kaolin as a silica-alumina raw material, preferably, the calcined kaolin used in the present invention is obtained by calcining kaolin ore at 650-700℃.

[0025] In this invention, the source of the calcined kaolin is limited to a wide range. It can be obtained by self-production using conventional methods or by commercially purchased products, as long as the above-mentioned calcination temperature and particle size limits are met.

[0026] According to the present invention, the activator can be any conventional alkali activator used in the preparation of geopolymers. Preferably, the activator is selected from alkali metal hydroxides and / or alkali metal silicates, and more preferably from alkali metal hydroxides and alkali metal silicates.

[0027] In this invention, the alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide; the alkali metal silicate is selected from sodium silicate and / or potassium silicate.

[0028] According to the present invention, the dispersant is selected from sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, preferably sodium tripolyphosphate.

[0029] According to the present invention, the co-solvent is selected from ethylene glycol and / or propylene glycol.

[0030] According to the present invention, the reinforcing agent can enhance the formation of the anionic precursor Al(OH) during the reaction of the silicon-aluminum raw material and the activator. 4- The polymerization rate of -OSi(OH)3 and -OSi(OH)2O- is increased, thereby improving the cured strength of the final geopolymer. Preferably, the reinforcing agent is selected from sodium fluoroaluminate and / or sodium fluorosilicate, and more preferably sodium fluoroaluminate.

[0031] According to the present invention, the defoamer is selected from silicone defoamers and / or polyether defoamers.

[0032] The geopolymer raw material composition provided by this invention, when mixed with water, yields a geopolymer precursor slurry, which, after curing, produces the geopolymer. The aluminosilicate raw material in the composition, after particle size screening, exhibits moderate reactivity. Furthermore, by modifying it with a surface modifier in the composition, a modified aluminosilicate raw material with locally hydrophobic surfaces and reduced surface functional groups is obtained. During subsequent slurry preparation and reaction with an activator, this modified aluminosilicate raw material exhibits a significantly reduced alkali solubility rate, thereby slowing down the reaction process and delaying the curing time of the precursor slurry. In addition, the surface modifier can be hydrolyzed into phosphate groups, also possessing a certain retarding effect. Using the composition of this invention as raw material to prepare geopolymers, the geopolymer precursor slurry can achieve a curing time greater than 120 min and a flowability greater than 18 cm at 60-100℃. After 1 day of curing, the compressive strength of the geopolymer is greater than 7 MPa, and after 3 days of curing, the compressive strength is greater than 14 MPa.

[0033] In this invention, the surface modifier is used to modify the aluminosilicate raw material using conventional mixing or kneading methods. For example, the surface modifier and the aluminosilicate raw material can be placed in a high-speed mixer according to the proportions in the composition, and mixed at high speed. The resulting mixture is the modified aluminosilicate raw material. The conditions for the modification treatment include: a stirring speed of 300-800 rpm and a mixing time of 0.5-1.5 h.

[0034] A second aspect of the present invention provides a geopolymer precursor slurry, which comprises: water, modified silica-alumina raw material, activator, dispersant, cosolvent, reinforcing agent and defoamer;

[0035] The modified aluminosilicate raw material is obtained by modifying the aluminosilicate raw material with a surface modifier; the surface modifier is a phthalate coupling agent.

[0036] Relative to 100 parts by weight of the aluminosilicate raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, the defoamer is 0.1-1 parts by weight, and the water is 50-100 parts by weight.

[0037] According to the present invention, the components in the geopolymer precursor slurry, based on satisfying the above-mentioned quantitative relationships, preferably, relative to 100 parts by weight of the aluminosilicate raw material, are: 4-6 parts by weight of the surface modifier, 30-60 parts by weight of the activator, 0.4-0.6 parts by weight of the dispersant, 8-15 parts by weight of the cosolvent, 2-3 parts by weight of the reinforcing agent, 0.4-0.6 parts by weight of the defoamer, and 70-80 parts by weight of water.

[0038] According to the present invention, the phthalate coupling agent is selected from at least one of pyrophosphate-type monoalkoxy titanates, bis(dioctyloxypyrophosphate) ethylene titanate, and isopropyltris(dodecylbenzenesulfonyl) titanate, preferably a pyrophosphate-type monoalkoxy titanate. The phthalate coupling agent can achieve surface modification of the aluminosilicate raw material, resulting in a modified aluminosilicate raw material with locally hydrophobic surfaces and a reduced number of surface functional groups, thereby significantly reducing the alkali solubility rate of the aluminosilicate raw material.

[0039] According to the present invention, the modification treatment can be carried out using conventional mixing modification or kneading modification methods. For example, the surface modifier and the aluminosilicate raw material can be placed in a high-speed mixer according to the above proportion and mixed by high-speed stirring. The resulting mixture is the modified aluminosilicate raw material. The conditions for the modification treatment include: a stirring speed of 300-800 rpm and a stirring time of 0.5-1.5 h.

[0040] According to the present invention, the aluminosilicate raw material can be any conventional active aluminosilicate oxide material used in the preparation of geopolymers. Preferably, the aluminosilicate raw material is selected from at least one of calcined kaolin, fly ash, and blast furnace slag, and more preferably calcined kaolin.

[0041] According to this method, for the purpose of controlling the reactivity of the aluminosilicate raw material, preferably, the average particle size of the aluminosilicate raw material is 200-325 mesh.

[0042] According to the present invention, the calcined kaolin is obtained by calcining kaolin ore at high temperature. Generally, kaolin ore exhibits activity after calcination at 600-850℃, with the strongest activity after calcination at 700-750℃. To control the reactivity of the calcined kaolin as a silica-alumina raw material, preferably, the calcined kaolin used in the present invention is obtained by calcining kaolin ore at 650-700℃.

[0043] In this invention, the source of the calcined kaolin is limited to a wide range. It can be obtained by self-production using conventional methods or by commercially purchased products, as long as the above-mentioned calcination temperature and particle size limits are met.

[0044] According to the present invention, the activator can be any conventional alkali activator used in the preparation of geopolymers. Preferably, the activator is selected from alkali metal hydroxides and / or alkali metal silicates, and more preferably from alkali metal hydroxides and alkali metal silicates.

[0045] In this invention, the alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide; the alkali metal silicate is selected from sodium silicate and / or potassium silicate.

[0046] According to the present invention, the dispersant is selected from at least one of sodium tripolyphosphate, sodium hexametaphosphate and sodium pyrophosphate, preferably sodium tripolyphosphate.

[0047] According to the present invention, the co-solvent is selected from ethylene glycol and / or propylene glycol.

[0048] According to the present invention, the reinforcing agent can enhance the formation of the anionic precursor Al(OH) during the reaction of the silicon-aluminum raw material and the activator. 4- The polymerization rate of -OSi(OH)3 and -OSi(OH)2O- is increased, thereby improving the cured strength of the final geopolymer. Preferably, the reinforcing agent is selected from sodium fluoroaluminate and / or sodium fluorosilicate, and more preferably sodium fluoroaluminate.

[0049] According to the present invention, the defoamer is selected from silicone defoamers and / or polyether defoamers.

[0050] The geopolymer precursor slurry provided by this invention contains modified aluminosilicate raw materials obtained by modifying aluminosilicate raw materials after particle size screening using a specific surfactant. The aluminosilicate raw materials, after particle size screening to control specific surface area and activity, and further modification, exhibit locally hydrophobic surface regions and a reduced number of surface functional groups, resulting in a significantly reduced alkali solubility rate. This, in turn, slows down the reaction process with the activator in the precursor slurry system. Furthermore, the phosphate groups, hydrolysis products of the surface modifier, also have a certain retarding effect. Therefore, the geopolymer precursor slurry of this invention possesses delayed curing properties and maintains excellent retarding effect even at high temperatures. Specifically, the geopolymer precursor slurry has a curing time greater than 120 min at 60-100℃, a flowability greater than 18 cm, a compressive strength greater than 7 MPa after 1 day of curing, and a compressive strength greater than 14 MPa after 3 days of curing.

[0051] According to a preferred embodiment of the present invention, the geopolymer precursor slurry has a curing time of more than 170 min and a flowability of more than 18 cm under conditions of 60-100℃. After curing for 1 day, the compressive strength of the geopolymer is greater than 8 MPa, and after curing for 3 days, the compressive strength of the geopolymer is greater than 16 MPa.

[0052] According to the present invention, the geopolymer precursor slurry can be prepared by mixing its constituent components. For example, the activator, dispersant, defoamer, cosolvent, reinforcing agent, and modified aluminosilicate raw material (obtained by modifying the aluminosilicate raw material with the surface modifier) ​​are added sequentially to water and stirred thoroughly according to the proportions defined above, and the resulting homogeneous mixture is the geopolymer precursor slurry.

[0053] The third aspect of this invention provides the application of the geopolymer precursor slurry described in the second aspect above in high-temperature cementing.

[0054] According to the present invention, the geopolymer precursor slurry has delayed curing properties, which can meet the needs of cementing operations in oil and gas wells. It is especially suitable for cementing operations in high-temperature wells such as heavy oil steam extraction, fire-fired heavy oil, shale oil in-situ extraction, hot dry rock, and ultra-deep wells, and has broad application prospects.

[0055] A fourth aspect of the present invention provides a method for high-temperature cementing, wherein the method includes: injecting the geopolymer precursor slurry described in the second aspect below into the well, obtaining a geopolymer after solidification, and using the geopolymer for cementing;

[0056] Curing conditions include: temperature of 60-100℃ and pressure of 21-60MPa.

[0057] According to the present invention, in the high-temperature cementing method, the geopolymer precursor slurry has a curing time of more than 120 min and a flowability of more than 18 cm under conditions of 60-100℃. After curing for 1 day, the compressive strength of the geopolymer is greater than 7 MPa, and after curing for 3 days, the compressive strength of the geopolymer is greater than 14 MPa.

[0058] The present invention will be described in detail below through examples. In the following examples and comparative examples, the flowability was measured according to the method specified in GB / T8077-2012;

[0059] Compressive strength: Measured according to the method specified in GB / T 19139-2012;

[0060] Curing time: Measured according to the method specified in GB / T 19139-2012.

[0061] Unless otherwise specified, all materials used are common commercially available products.

[0062] Example 1

[0063] Preparation of calcined kaolin: Kaolin ore is crushed and ground, and kaolin powder with an average particle size of 325 mesh is screened out. It is then calcined at 680℃ for 2 hours and naturally cooled to room temperature to obtain calcined kaolin (325 mesh).

[0064] The geological polymer raw material composition used is as follows: calcined kaolin (100 parts by weight), pyrophosphate type monoalkoxy titanate (5 parts by weight), sodium hydroxide (20 parts by weight), sodium silicate (20 parts by weight), sodium tripolyphosphate (0.5 parts by weight), ethylene glycol (10 parts by weight), sodium fluoroaluminate (2 parts by weight) and organosilicon defoamer (0.5 parts by weight).

[0065] Preparation of geopolymer precursor slurry: All of the calcined kaolin and pyrophosphate-type monoalkoxy titanate in the above composition were placed in a high-speed mixer and stirred at 700 rpm for 1 hour at room temperature to obtain modified calcined kaolin; 80 parts by weight of water were taken, and all of the sodium hydroxide, sodium silicate, sodium tripolyphosphate, organosilicon defoamer, ethylene glycol and sodium fluoroaluminate in the above composition were added in sequence and stirred and mixed. Then, all of the above modified calcined kaolin was added and stirred and mixed evenly to obtain geopolymer precursor slurry (denoted as S1).

[0066] The flowability of S1 is 20 cm. S1 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 1.

[0067] Table 1

[0068]

[0069] Example 2

[0070] Calcined kaolin was prepared according to the method and parameters of Example 1.

[0071] The geopolymer raw material composition used is as follows: calcined kaolin (100 parts by weight), pyrophosphate type monoalkoxy titanate (6 parts by weight), sodium hydroxide (25 parts by weight), sodium silicate (30 parts by weight), sodium tripolyphosphate (0.6 parts by weight), ethylene glycol (13 parts by weight), sodium fluoroaluminate (3 parts by weight) and organosilicon defoamer (0.6 parts by weight).

[0072] Using the above-described geopolymer raw material composition, a geopolymer precursor slurry was prepared according to the method and parameters of Example 1, except that the water content was 70 parts by weight. All other conditions were the same as in Example 1. A geopolymer precursor slurry (denoted as S2) was obtained.

[0073] The flowability of S2 is 20 cm. S2 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 2.

[0074] Table 2

[0075]

[0076] Example 3

[0077] Calcined kaolin was prepared according to the method and parameters of Example 1.

[0078] The geopolymer raw material composition used is as follows: calcined kaolin (100 parts by weight), bis(dioctyloxypyrophosphate) ethylene titanate (10 parts by weight), sodium hydroxide (30 parts by weight), sodium silicate (50 parts by weight), sodium hexametaphosphate (1 part by weight), propylene glycol (20 parts by weight), sodium fluoroaluminate (5 parts by weight) and organosilicon defoamer (1 part by weight).

[0079] Using the above-mentioned geopolymer raw material composition, a geopolymer precursor slurry was prepared according to the method and parameters of Example 1, except that the water content was 50 parts by weight. All other conditions were the same as in Example 1. A geopolymer precursor slurry (denoted as S3) was obtained.

[0080] The flowability of S3 was 19 cm. S3 was cured at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained 1 day and 3 days after curing were recorded. The results are shown in Table 3.

[0081] Table 3

[0082]

[0083]

[0084] Example 4

[0085] Calcined kaolin was prepared according to the method and parameters of Example 1.

[0086] The geological polymer raw material composition used is as follows: calcined kaolin (100 parts by weight), isopropyl tris(dodecylbenzenesulfonyl) titanate (1 part by weight), sodium hydroxide (3 parts by weight), sodium silicate (5 parts by weight), sodium pyrophosphate (0.1 parts by weight), propylene glycol (2 parts by weight), sodium fluorosilicate (0.5 parts by weight) and organosilicon defoamer (0.1 parts by weight).

[0087] Using the above-described geopolymer raw material composition, a geopolymer precursor slurry was prepared according to the method and parameters of Example 1, except that the water content was 50 parts by weight. All other conditions were the same as in Example 1. A geopolymer precursor slurry (denoted as S4) was obtained.

[0088] The flowability of S4 is 19 m. S4 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 4.

[0089] Table 4

[0090]

[0091] Example 5

[0092] Calcined kaolin was prepared according to the method in Example 1, except that the calcination temperature was 750°C.

[0093] The geological polymer raw material composition used is as follows: calcined kaolin (100 parts by weight), pyrophosphate type monoalkoxy titanate (5 parts by weight), sodium hydroxide (20 parts by weight), sodium silicate (20 parts by weight), sodium tripolyphosphate (0.5 parts by weight), ethylene glycol (10 parts by weight), sodium fluoroaluminate (2 parts by weight) and organosilicon defoamer (0.5 parts by weight).

[0094] Using the above-mentioned geopolymer raw material composition, a geopolymer precursor slurry (denoted as S5) was prepared according to the method and parameters of Example 1.

[0095] The flowability of S5 is 14 cm. S5 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 5.

[0096] Table 5

[0097]

[0098] Note: "-" indicates that the curing time has not met the requirements, and strength data will not be measured.

[0099] Example 6

[0100] 200-mesh fly ash was used as the silica-alumina raw material.

[0101] The geopolymer raw material composition used is as follows: fly ash (100 parts by weight), pyrophosphate type monoalkoxy titanate (5 parts by weight), sodium hydroxide (20 parts by weight), sodium silicate (20 parts by weight), sodium tripolyphosphate (0.5 parts by weight), ethylene glycol (10 parts by weight), sodium fluoroaluminate (2 parts by weight) and organosilicon defoamer (0.5 parts by weight).

[0102] Using the above-mentioned geopolymer raw material composition, a geopolymer precursor slurry (denoted as S6) was prepared according to the method and parameters of Example 1.

[0103] The flowability of S6 is 19 cm. S6 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 6.

[0104] Table 6

[0105]

[0106] Note: "-" indicates that the curing time has not met the requirements, and strength data will not be measured.

[0107] Comparative Example 1

[0108] Calcined kaolin was prepared according to the method in Example 1.

[0109] Geopolymer raw material composition: The pyrophosphate type monoalkoxy titanate in the geopolymer raw material composition of Example 1 was replaced with an equal weight of silane coupling agent KH570, while other components and contents remained unchanged.

[0110] Using the above-mentioned geopolymer raw material composition, a geopolymer precursor slurry (denoted as D1) was prepared according to the method of Example 1.

[0111] The flowability of D1 is 19 cm. D1 was tested at 60℃, 70℃, 80℃, 90℃, and 100℃ (all at 40 MPa), and the curing time and compressive strength of the geopolymer obtained after 1 day and 3 days of curing were recorded. The results are shown in Table 7.

[0112] Table 7

[0113]

[0114] Note: "-" indicates that the curing time has not met the requirements, and strength data will not be measured.

[0115] As shown in Tables 1-7, the geopolymer precursor slurry prepared using the geopolymer raw material composition of the present invention has a flowability greater than 18 cm, a curing time greater than 120 min at 60-100℃, a compressive strength greater than 7 MPa after 1 day of curing, and a compressive strength greater than 14 MPa after 3 days of curing. This effectively meets the requirements for curing time and strength of the geopolymer precursor slurry in cementing operations and achieves good flowability. Examples 1-2 show a greater overall advantage in terms of curing time and strength. Example 3 uses a geopolymer raw material composition containing more surface modifiers than Examples 1-2, significantly reducing the surface activity of the raw material and further extending the curing time. Example 4 uses a geopolymer raw material composition containing less surface modifiers than Examples 1-3, resulting in a relatively shorter curing time and increased strength under the same experimental conditions. The calcined kaolin in Example 5 has excessively high activity, making it difficult to achieve good curing time control. Comparative Example 1 did not use phthalate coupling agents in its geopolymer raw material composition, thus failing to achieve the effects of the present invention.

[0116] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A geopolymer raw material composition, characterized in that, The geopolymer raw material composition comprises: aluminosilicate raw material, a surface modifier, an activator, a dispersant, a cosolvent, a reinforcing agent, and a defoamer; relative to 100 parts by weight of the aluminosilicate raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, and the defoamer is 0.1-1 parts by weight; The surface modifier is a titanate coupling agent; The titanate coupling agent is a pyrophosphate-type monoalkoxy titanate and / or a bis(dioctyloxypyrophosphate) ethylene titanate. The silicon-aluminum raw material is selected from calcined kaolin; The calcined kaolin is obtained by calcining kaolin ore at 650-700℃.

2. The geopolymer raw material composition according to claim 1, wherein, Relative to 100 parts by weight of the aluminosilicate raw material, the surface modifier is 4-6 parts by weight, the activator is 30-60 parts by weight, the dispersant is 0.4-0.6 parts by weight, the cosolvent is 8-15 parts by weight, the reinforcing agent is 2-3 parts by weight, and the defoamer is 0.4-0.6 parts by weight.

3. The geopolymer raw material composition according to claim 1 or 2, wherein, The titanate coupling agent is a pyrophosphate-type monoalkoxy titanate.

4. The geopolymer raw material composition according to claim 1 or 2, wherein the average particle size of the silica-alumina raw material is 200-325 mesh.

5. The geopolymer raw material composition according to claim 1 or 2, wherein, The activator is selected from alkali metal hydroxides and / or alkali metal silicates.

6. The geopolymer raw material composition according to claim 5, wherein, The activator is selected from alkali metal hydroxides and alkali metal silicates.

7. The geopolymer raw material composition according to claim 5, wherein, The alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide; the alkali metal silicate is selected from sodium silicate and / or potassium silicate.

8. The geopolymer raw material composition according to claim 1 or 2, wherein, The dispersant is selected from at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate.

9. The geopolymer raw material composition according to claim 1 or 2, wherein, The co-solvent is selected from ethylene glycol and / or propylene glycol.

10. The geopolymer raw material composition according to claim 1 or 2, wherein, The reinforcing agent is selected from sodium fluoroaluminate and / or sodium fluorosilicate.

11. The geopolymer raw material composition according to claim 10, wherein, The reinforcing agent is sodium fluoroaluminate.

12. The geopolymer raw material composition according to claim 1 or 2, wherein, The defoamer is selected from silicone defoamers and / or polyether defoamers.

13. A geopolymer precursor slurry, characterized in that, The geopolymer precursor slurry comprises: water, modified silica-alumina raw materials, activator, dispersant, cosolvent, reinforcing agent, and defoamer; The modified aluminosilicate raw material is obtained by modifying the aluminosilicate raw material with a surface modifier; the surface modifier is a titanate coupling agent. Relative to 100 parts by weight of the silica-alumina raw material, the surface modifier is 1-10 parts by weight, the activator is 8-80 parts by weight, the dispersant is 0.1-1 parts by weight, the cosolvent is 2-20 parts by weight, the reinforcing agent is 0.5-5 parts by weight, the defoamer is 0.1-1 parts by weight, and the water is 50-100 parts by weight; The titanate coupling agent is a pyrophosphate-type monoalkoxy titanate and / or a bis(dioctyloxypyrophosphate) ethylene titanate. The silicon-aluminum raw material is selected from calcined kaolin; The calcined kaolin is obtained by calcining kaolin ore at 650-700℃.

14. The geopolymer precursor slurry according to claim 13, wherein, Relative to 100 parts by weight of the aluminosilicate raw material, the surface modifier is 4-6 parts by weight, the activator is 30-60 parts by weight, the dispersant is 0.4-0.6 parts by weight, the cosolvent is 8-15 parts by weight, the reinforcing agent is 2-3 parts by weight, the defoamer is 0.4-0.6 parts by weight, and the water is 70-80 parts by weight.

15. The geopolymer precursor slurry according to claim 13 or 14, wherein, The titanate coupling agent is a pyrophosphate-type monoalkoxy titanate.

16. The geopolymer precursor slurry according to claim 13 or 14, wherein, The average particle size of the silicon-aluminum raw material is 200-325 mesh.

17. The geopolymer precursor slurry according to claim 13 or 14, wherein, The activator is selected from alkali metal hydroxides and / or alkali metal silicates.

18. The geopolymer precursor slurry according to claim 17, wherein, The activator is an alkali metal hydroxide and an alkali metal silicate.

19. The geopolymer precursor slurry according to claim 18, wherein, The alkali metal hydroxide is selected from sodium hydroxide and / or potassium hydroxide; the alkali metal silicate is selected from sodium silicate and / or potassium silicate.

20. The geopolymer precursor slurry according to claim 13 or 14, wherein, The dispersant is selected from at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate.

21. The geopolymer precursor slurry according to claim 13 or 14, wherein, The co-solvent is selected from ethylene glycol and / or propylene glycol.

22. The geopolymer precursor slurry according to claim 13 or 14, wherein, The reinforcing agent is selected from sodium fluoroaluminate and / or sodium fluorosilicate.

23. The geopolymer precursor slurry according to claim 22, wherein, The reinforcing agent is selected from sodium fluoroaluminate.

24. The geopolymer precursor slurry according to claim 13 or 14, wherein, The defoamer is selected from silicone defoamers and / or polyether defoamers.

25. The geopolymer precursor slurry according to claim 13 or 14, wherein, The geopolymer precursor slurry has a curing time of more than 120 min and a flowability of more than 18 cm under conditions of 60-100℃. The geopolymer obtained after curing for 1 day has a compressive strength of more than 7 MPa, and the geopolymer obtained after curing for 3 days has a compressive strength of more than 14 MPa.

26. The application of the geopolymer precursor slurry according to any one of claims 13-25 in high-temperature cementing.

27. A method for high-temperature cementing, wherein, The method includes: injecting the geopolymer precursor slurry according to any one of claims 13-25 downhole, obtaining the geopolymer after solidification, and using the geopolymer for cementing; Curing conditions include: temperature of 60-100℃ and pressure of 21-60MPa.

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