Setting regulator for cement-clay two-component grouting material, preparation method and application

Abstract

The invention discloses a setting regulator for cement-clay two-component grouting material, a preparation method, and applications. The setting regulator comprises dodecaluminate heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine, and diphenylmethane diisocyanate. The prepared setting regulator has excellent performance and can achieve precise control of setting time under different environments, enabling the grouting material to maintain high performance under a wider range of environmental conditions, reducing construction difficulty, reducing material waste, and improving construction efficiency.

Description

Technical Field

[0001] The present invention relates to the technical field of setting regulators, and in particular to a setting regulator for cement-clay two-component grouting material, a preparation method and an application thereof. Background Art

[0002] Cement-clay two-component grouting material is a composite material widely used in the treatment of coal mine ash floor. This material usually consists of cement as the main gelling component, supplemented by mineral additives such as clay to reduce costs and improve its adaptability and performance under complex geological conditions. Its main uses include: (1) Improving the stability of stratum cracks and pores and enhancing the bearing capacity of rock and soil. (2) Filling and consolidating in stratum cracks and pores to achieve water blocking or reinforcement. (3) Filling cavities and cracks in mines to prevent gas leakage and groundwater infiltration.

[0003] Although cement-clay two-component grouting materials have been widely used in engineering, some problems still exist in terms of setting time: (1) Difficulty in controlling setting time: Traditional setting agents are difficult to accurately control the setting time in complex environments. (2) Poor environmental adaptability: The performance of traditional grouting materials will be affected under low temperature or high pressure conditions. (3) Construction complexity: Precise proportions and complex construction processes are required, which increases the difficulty and cost of construction. Summary of the Invention

[0004] The embodiments of the present application provide a setting regulator, preparation method, and application for cement-clay two-component grouting materials. The setting regulator is composed of dodecaluminate heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride, and N,N-dimethylethanolamine. The prepared setting regulator has excellent performance and can achieve precise control of setting time under different environments, so that the grouting material maintains high performance under a wider range of environmental conditions, reduces construction difficulty, reduces material waste, and improves construction efficiency.

[0005] The invention provides a setting regulator for cement-clay two-component grouting material. The setting regulator consists of dodecalcium heptaaluminate, nano aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine and diphenylmethane diisocyanate.

[0006] In some embodiments, the components of the setting agent include, by mass, 40-60 parts of dodecaaluminate, 5-10 parts of nano-aluminum sol, 20-30 parts of aluminum sulfate, 5-10 parts of polyaluminum calcium chloride, 5-10 parts of N,N-dimethylethanolamine, and 0.01-0.05 parts of diphenylmethane diisocyanate (MDI).

[0007] The present invention also provides a method for preparing a setting regulator for cement-clay two-component grouting material, comprising:

[0008] Adding polyaluminium calcium chloride to the nano-aluminium sol, heating to a preset temperature, stirring at the preset temperature for a first preset time, and cooling to room temperature after stirring to form a first mixed solution;

[0009] adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for a second preset time to form a second mixed solution;

[0010] drying the second mixed solution for a third preset time to obtain a target powder;

[0011] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting regulator.

[0012] In some embodiments, the preset temperature is 80°C.

[0013] In some embodiments, the first preset duration is 20 minutes.

[0014] In some embodiments, the second preset duration is 10 minutes.

[0015] In some embodiments, the drying temperature is 40°C.

[0016] In some embodiments, the third preset duration is 24 hours.

[0017] The present invention also provides an application of a setting regulator for cement-clay two-component grouting material. The setting regulator is applied to the cement-clay two-component grouting material in which cement accounts for more than 40% of the total solid phase mass.

[0018] In some embodiments, the setting regulator accounts for 5-10% of the mass of the cement-clay two-component grouting material.

[0019] The present invention provides a setting regulator for cement-clay two-component grouting material, a preparation method, and an application thereof. The setting regulator comprises dodecaluminate heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine, and diphenylmethane diisocyanate. The prepared setting regulator has excellent performance, can achieve precise control of setting time under different environments, enables the grouting material to maintain high performance under a wider range of environmental conditions, reduces construction difficulty, reduces material waste, and improves construction efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 A flow chart of a method for preparing a setting regulator for cement-clay two-component grouting material according to some embodiments is exemplified. DETAILED DESCRIPTION

[0021] In order to better understand the above technical solution, the technical solution of this application is described in detail below through specific implementation methods.

[0022] In order to solve the above technical problems, an embodiment of the present application provides a setting regulator for cement-clay two-component grouting material, which is composed of dodecaluminate heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine and diphenylmethane diisocyanate. It has excellent setting performance and can achieve precise control of setting time under different environments; enable the grouting material to maintain high performance under a wider range of environmental conditions; reduce construction difficulty, reduce material waste, and improve construction efficiency.

[0023] In the embodiment of the present application, dodecalcium heptaaluminate and aluminum sulfate are the main components of the setting agent, both of which play a role in promoting the coagulation of the grouting material. Dodecalcium heptaaluminate dissolves and hydrates earlier than aluminum sulfate, forming a gradient relay with aluminum sulfate, better providing aluminum ions and calcium ions to the grouting material, thereby forming an ettringite skeleton with the silicate ions in the grouting material, playing a coagulation role.

[0024] Nano-aluminum sol is a material that dissolves faster than calcium dodecaaluminate heptaaluminate. It is an enhanced component of the setting agent and mainly plays a role in strengthening the setting of the grouting material. By adjusting the mass range of the nano-aluminum sol, the effect of the setting agent on the setting time of the grouting material can be adjusted.

[0025] On the one hand, polyaluminium calcium chloride provides chloride ions and calcium ions, and on the other hand, it provides macromolecular side chains, allowing the hydration product calcium aluminate to better connect with the inactive substances in the grouting material to form a three-dimensional network structure.

[0026] On the one hand, N,N-dimethylethanolamine promotes the dissolution of active substances (silicate) in the grouting material and promotes the dispersion of the above-mentioned substances; on the other hand, it forms hydrogen bonds with the crystal water in the ettringite, better stabilizing the overlap between the ettringites and making the grouting material more stable in the later stage.

[0027] The isocyanate group (-NCO) in diphenylmethane diisocyanate is highly reactive and reacts with the hydroxyl and amino groups of N,N-dimethylethanolamine. Isocyanate reacts with hydroxyl groups to form carbamate bonds, and with amino groups to form urea bonds. Through these reactions, isocyanate compounds can be alternately linked with N,N-dimethylethanolamine to form chain polymers with a certain molecular weight.

[0028] In some embodiments, the components of the setting agent include, by mass, 40-60 parts of dodecaaluminate, 5-10 parts of nano-aluminum sol, 20-30 parts of aluminum sulfate, 5-10 parts of polyaluminum calcium chloride, 5-10 parts of N,N-dimethylethanolamine, and 0.01-0.05 parts of diphenylmethane diisocyanate.

[0029] The mass ratios of dodecalcium heptaaluminate and aluminum sulfate are 40-60 and 20-30 respectively. Both are the main components of the setting agent. Aluminum sulfate dissolves slower than dodecalcium heptaaluminate. If the mass ratio of aluminum sulfate is higher and the mass ratio of dodecalcium heptaaluminate is lower, the aluminum ions generated in the early stage will be less, which is not conducive to setting. If the mass ratio of aluminum sulfate is too low and the mass ratio of dodecalcium heptaaluminate is higher, it does not meet the requirements of gradient setting, and will cause the slurry to coagulate faster, which does not meet the grouting requirements.

[0030] Nano-alumina sol is expensive and dissociates aluminum ions very quickly. Too much leads to rapid coagulation and high costs, while too little has no coagulation-promoting effect. Therefore, the nano-alumina sol is set at 5-10 parts. Polyaluminum calcium chloride, like nano-alumina sol, is also expensive and dissociates aluminum ions very quickly, so the polyaluminum calcium chloride is set at 5-10 parts.

[0031] N,N-dimethylethanolamine is a key material that plays many roles that other substances cannot (increasing solubility, increasing dispersion, forming hydrogen bonds to increase linkage), but its price is too high. Too much will result in high costs, while too little will not be effective, so it is set to 5-10 parts.

[0032] Figure 1 The present invention provides a method for preparing a setting regulator for cement-clay two-component grouting material, comprising:

[0033] S100, adding polyaluminium calcium chloride to the nano-aluminium sol and heating it to a preset temperature, stirring it at the preset temperature for a first preset time, and cooling it to room temperature after stirring to form a first mixed solution.

[0034] Polyaluminum calcium chloride added to nano aluminum sol is a substance whose aluminum ions are easily dissociated but difficult to disperse. It is difficult to cause agglomeration and flocculation with other substances by mixing them first, and then heat them to depolymerize the polyaluminum calcium chloride and disperse it better.

[0035] In the embodiments of the present application, polyaluminium calcium chloride is added to the nano-aluminium sol, heated to a preset temperature, and then stirred at a constant temperature for a first preset time. In some embodiments, the preset temperature is 80°C. If the temperature is too high or the stirring time is too long, the degree of depolymerization will be too high, and the effect will be lost. If the temperature is too low, the depolymerization will be difficult, and the time process may even affect the preparation efficiency.

[0036] In some embodiments, the first preset duration is 20 minutes.

[0037] S200: Add N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stir for a second preset time to form a second mixed solution. In some embodiments, the second preset time is 10 minutes. Adding N,N-dimethylethanolamine is to promote dispersion of the two substances. Stirring for 10 minutes is also a suitable time. Stirring for too long will affect preparation efficiency, while stirring for too short a time will not be effective.

[0038] S300: Dry the second mixed solution for a third preset time to obtain a target powder. In some embodiments, the drying temperature is 40° C. In some embodiments, the third preset time is 24 hours.

[0039] S400, uniformly mixing the target powder, dodecacalcium heptaaluminate and aluminum sulfate to obtain a setting agent.

[0040] The present invention also provides a use of the aforementioned setting regulator for cement-clay two-component grouting material, wherein the setting regulator is applied to a cement-clay two-component grouting material in which cement accounts for more than 40% of the total solid phase mass. In some embodiments, the setting regulator accounts for 5-10% of the mass of the cement-clay two-component grouting material.

[0041] In the embodiment of the present application, the setting regulator accounts for 5-10% of the mass of the cement-clay two-component grouting material during use. The setting regulator is only applicable to grouting materials in which cement accounts for more than 40% of the total solid phase mass.

[0042] Example 1

[0043] The components in the setting agent include, by mass, 40 parts of dodecaluminate heptaaluminate, 10 parts of nano-aluminum sol, 30 parts of aluminum sulfate, 10 parts of polyaluminum calcium chloride, 10 parts of N,N-dimethylethanolamine and 0.01 parts of diphenylmethane diisocyanate.

[0044] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0045] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0046] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0047] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0048] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is used in grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0049] Example 2

[0050] The components in the setting agent include, by mass, 50 parts of dodecaluminate heptaaluminate, 8 parts of nano-aluminum sol, 26 parts of aluminum sulfate, 8 parts of polyaluminum calcium chloride, 8 parts of N,N-dimethylethanolamine and 0.03 parts of diphenylmethane diisocyanate.

[0051] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0052] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0053] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0054] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0055] When used, the setting regulator accounts for 8% of the mass of the cement-clay two-component grouting material. The setting regulator is used in grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0056] Example 3

[0057] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 10 parts of nano-aluminum sol, 20 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride, 5 parts of N,N-dimethylethanolamine and 0.05 parts of diphenylmethane diisocyanate.

[0058] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0059] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0060] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0061] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0062] When in use, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applicable to grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0063] Example 4

[0064] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 5 parts of nano-aluminum sol, 25 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride, 5 parts of N,N-dimethylethanolamine and 0.03 parts of diphenylmethane diisocyanate.

[0065] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0066] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0067] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0068] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0069] When in use, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applicable to grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0070] Example 5

[0071] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 5 parts of nano-aluminum sol, 25 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride, 5 parts of N,N-dimethylethanolamine and 0.03 parts of diphenylmethane diisocyanate.

[0072] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0073] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0074] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0075] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0076] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is used in grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0077] Comparative Example 1

[0078] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 5 parts of nano-aluminum sol, 25 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride and 0.03 parts of diphenylmethane diisocyanate.

[0079] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0080] adding diphenylmethane diisocyanate to the first mixed solution and stirring for 20 minutes to form a second mixed solution;

[0081] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0082] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0083] When in use, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applicable to grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0084] Comparative Example 2

[0085] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 5 parts of nano-aluminum sol, 25 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride, 5 parts of N,N-dimethylethanolamine and 0.03 parts of diphenylmethane diisocyanate.

[0086] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol and stirring for 20 minutes to form a first mixed solution;

[0087] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0088] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0089] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0090] When in use, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applicable to grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0091] Comparative Example 3

[0092] Grouting materials in which no setting regulator is added and the cement accounts for more than 40% of the total solid phase mass.

[0093] Comparative Example 4

[0094] The components in the setting agent include, by mass, 60 parts of dodecaluminate heptaaluminate, 5 parts of nano-aluminum sol, 25 parts of aluminum sulfate, 5 parts of polyaluminum calcium chloride and 5 parts of N,N-dimethylethanolamine.

[0095] The preparation method of the coagulant is as follows: adding polyaluminium calcium chloride to nano-aluminium sol, heating to 80°C, stirring at a constant temperature of 80°C for 20 minutes, and cooling to room temperature after stirring to form a first mixed solution;

[0096] Adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for 10 minutes to form a second mixed solution;

[0097] The second mixed solution was dried at 40°C for 24 hours to obtain the target powder;

[0098] The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent.

[0099] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is used in grouting materials in which the cement accounts for more than 40% of the total solid phase mass.

[0100] The following table describes the components of the setting agent, the main process parameters used in its preparation, and the test results of setting time and compressive strength, as shown in Table 1. The test materials used in the following examples were purchased from conventional stores unless otherwise specified. The quantitative tests in the following examples were performed in triplicate, and the data are presented as the mean or mean ± standard deviation of the three replicates.

[0101] Table 1

[0102]

[0103]

[0104] It can be seen from Example 4 and Comparative Example 4 that diphenylmethane diisocyanate can be alternately connected with N,N-dimethylethanolamine to synergize with each other and enhance the setting function of the setting regulator.

[0105] It can be seen from Example 4 and Comparative Example 3 that the addition of 10% setting regulator can advance the setting time of the grouting material by 14 hours.

[0106] It can be seen from Example 4 and Comparative Example 2 that if the setting regulator components are not stirred under a constant temperature environment of 80° C., the setting regulator effect will be reduced by 1 time.

[0107] It can be seen from Example 4 and Comparative Example 1 that if the setting agent component does not contain N,N-dimethylethanolamine, the setting effect will be reduced by 1 time.

[0108] In summary, the present invention provides a setting regulator, preparation method and application for cement-clay two-component grouting material. The setting regulator is composed of dodecalcium heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride and N,N-dimethylethanolamine. The prepared setting regulator has excellent performance and can achieve precise control of the setting time under different environments, so that the grouting material maintains high performance under a wider range of environmental conditions, reduces construction difficulty, reduces material waste, and improves construction efficiency.

[0109] It is easy for those skilled in the art to understand that, under the premise of no conflict, the above-mentioned advantageous methods can be freely combined and superimposed. The above is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present application should be included in the scope of protection of the present application. The above is only a preferred embodiment of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and variations can be made without departing from the technical principles of the present application. These improvements and variations should also be regarded as the scope of protection of the present application.

Claims

1. A setting regulator for cement-clay two-component grouting material, characterized in that: The coagulant is composed of dodecaluminate heptaaluminate, nano aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine and diphenylmethane diisocyanate; The components of the setting agent include, by mass, 40-60 parts of dodecaluminate heptaaluminate, 5-10 parts of nano-aluminum sol, 20-30 parts of aluminum sulfate, 5-10 parts of polyaluminum calcium chloride, 5-10 parts of N,N-dimethylethanolamine and 0.01-0.05 parts of diphenylmethane diisocyanate; The preparation method of the coagulant comprises: adding polyaluminum calcium chloride to nano aluminum sol, heating to a preset temperature, stirring at the preset temperature for a first preset time, and cooling to room temperature after stirring to form a first mixed solution; adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution, stirring for a second preset time, to form a second mixed solution; drying the second mixed solution for a third preset time to obtain a target powder; and uniformly mixing the target powder, dodecacalcium heptaaluminate, and aluminum sulfate to obtain a coagulant; wherein the preset temperature is 80° C.; and the first preset time is 20 minutes.

2. The method for preparing the setting regulator for cement-clay two-component grouting material according to claim 1, characterized in that: include: Adding polyaluminium calcium chloride to the nano-aluminium sol, heating to a preset temperature, stirring at the preset temperature for a first preset time, and cooling to room temperature after stirring to form a first mixed solution; adding N,N-dimethylethanolamine and diphenylmethane diisocyanate to the first mixed solution and stirring for a second preset time to form a second mixed solution; drying the second mixed solution for a third preset time to obtain a target powder; The target powder, dodecacalcium heptaaluminate and aluminum sulfate are uniformly mixed to obtain a setting agent; Among them, the preset temperature is 80°C; and the first preset time is 20 minutes.

3. The method according to claim 2, characterized in that The second preset time length is 10 minutes.

4. The method according to claim 2, characterized in that The drying temperature of the drying is 40°C.

5. The method according to claim 2, characterized in that The third preset duration is 24 hours.

6. The use of the setting regulator for cement-clay two-component grouting material according to claim 1, characterized in that: The setting regulator is applied to a cement-clay two-component grouting material in which cement accounts for more than 40% of the total solid phase mass.

7. The use according to claim 6, characterized in that The setting regulator accounts for 5-10% of the mass of the cement-clay two-component grouting material.

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