Condensing time control agent for cement-clay two-component grouting material as well as preparation method and application of thickening time control agent

Abstract

The invention discloses a thickening time control agent for a cement-clay two-component grouting material, a preparation method and application, the thickening time control agent is composed of dodecacalcium heptaaluminate, nano-alumina sol, aluminum sulfate, polyaluminum calcium chloride, N, N-dimethylethanolamine and diphenylmethane diisocyanate, the prepared thickening time control agent is excellent in performance, and the thickening time control agent has good application prospects. The setting time can be accurately controlled in different environments, so that the grouting material can keep high performance under wider environmental conditions, the construction difficulty is reduced, the material waste is reduced, and the construction efficiency is improved.

Description

Technical Field

[0001] The 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 application thereof. Background Art

[0002] Cement-clay two-component grouting material is a composite material widely used in the treatment of coal mine Ordovician 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, there are still some problems in setting: (1) Difficulty in controlling setting time: Traditional setting agents are difficult to accurately control 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 construction difficulty and cost. Summary of the invention

[0004] The embodiment of the present application provides a setting regulator, preparation method and application for cement-clay two-component grouting material. The setting regulator is composed of calcium dodecaaluminate, 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.

[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 in 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 (MDI).

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

[0008] 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;

[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 time length is 10 minutes.

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

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

[0017] The invention also provides an application of a setting regulator for cement-clay two-component grouting material, wherein 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 weight 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 consists of dodecalcium heptaaluminate, nano-aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine and diphenylmethane diisocyanate. The prepared setting regulator has excellent performance and can realize accurate 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. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

[0022] In order to solve the above technical problems, the 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, and has excellent setting performance. It can achieve precise control of the 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 embodiments 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 for the grouting material, thereby generating an ettringite skeleton with the silicate ions in the grouting material, thereby 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 grouting materials. By adjusting the mass range of nano-aluminum sol, the influence of the setting agent on the setting time of the grouting material can be adjusted.

[0025] Polyaluminium calcium chloride provides chloride ions and calcium ions on one hand, and macromolecular side chains on the other, 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 materials, and can also promote the dispersion of the above-mentioned substances; on the other hand, it forms hydrogen bonds with the crystal water in the ettringite to better stabilize the overlap between the ettringites and make the grouting materials more stable in the later stage.

[0027] The isocyanate group (-NCO) in diphenylmethane diisocyanate is highly reactive and can react with the hydroxyl and amino groups of N,N-dimethylethanolamine. Isocyanate reacts with hydroxyl groups to form carbamate bonds and reacts 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 in 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.

[0029] The mass proportions 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 proportion of aluminum sulfate is higher and the mass proportion 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 proportion of aluminum sulfate is too little and the mass proportion of dodecalcium heptaaluminate is higher, it does not meet the requirements of gradient setting, and the slurry will coagulate faster, which does not meet the requirements of grouting.

[0030] Nano aluminum sol is expensive and aluminum ions dissociate very quickly. Too much will cause coagulation and high cost, while too little will not promote coagulation, so the amount of nano aluminum sol is set at 5-10 parts. Polyaluminum calcium chloride is the same as nano aluminum sol, but its price is too high and aluminum ions dissociate very quickly, so the amount of polyaluminum calcium chloride is set at 5-10 parts.

[0031] N,N-dimethylethanolamine is a key material that plays a role that many other substances cannot (increasing solubility, increasing dispersion, forming hydrogen bonds to increase connectivity), but its price is too high. Too much will result in high costs, and too little will have no effect, so it is set to 5-10 parts.

[0032] Figure 1 The present invention exemplarily shows a flow chart of a method for preparing a setting regulator for a cement-clay two-component grouting material according to some embodiments. The present invention provides a method for preparing a setting regulator for a 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] Polyaluminium calcium chloride added to nano-aluminium sol is a substance whose aluminum ions are easily dissociated but not easily dispersed. It is difficult to agglomerate and flocculate with other substances by mixing them first, and then heat them to depolymerize the polyaluminium calcium chloride and disperse it better.

[0035] In the embodiment of the present application, after polyaluminium calcium chloride is added to the nano-aluminium sol and heated to a preset temperature, constant temperature stirring is performed for a first preset time. In some embodiments, the preset temperature is 80°C. If the temperature is too high or the time is too long, the degree of depolymerization will be too high and the effect will be lost, while if the temperature is too low, it will not be easy to depolymerize, and even the time process will affect the preparation efficiency.

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

[0037] S200, 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. In some embodiments, the second preset time is 10 minutes. Adding N, N-dimethylethanolamine is to promote the dispersion of the two substances. Ten minutes of stirring is also a more appropriate time. Too long will affect the preparation efficiency, and too short will not have any effect.

[0038] S300, drying 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 regulator.

[0040] The present invention provides another application of the setting regulator for cement-clay two-component grouting material, wherein the setting regulator is applied to 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 when used. 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 and heating to 80°C, stirring at 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 h to obtain the target powder;

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

[0048] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is applied to 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 and 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 h to obtain the target powder;

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

[0055] When used, the setting regulator accounts for 8% of the mass of the cement-clay two-component grouting material. The setting regulator is applied to 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 weight: 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 and 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 h to obtain the target powder;

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

[0062] When used, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applied 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 weight: 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 and heating to 80°C, stirring at 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 h to obtain the target powder;

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

[0069] When used, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applied 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 weight: 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 and heating to 80°C, stirring at 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 h to obtain the target powder;

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

[0076] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is applied to 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 weight: 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 and 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 h to obtain the target powder;

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

[0083] When used, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applied 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 weight: 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 into 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 h to obtain the target powder;

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

[0090] When used, the setting regulator accounts for 10% of the mass of the cement-clay two-component grouting material. The setting regulator is applied 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 cement accounts for more than 40% of the total solid mass.

[0093] Comparative Example 4

[0094] The components in the setting agent include, by weight: 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 and 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 h to obtain the target powder;

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

[0099] When used, the setting regulator accounts for 5% of the mass of the cement-clay two-component grouting material. The setting regulator is applied to 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 in the preparation of the setting agent, and the test results of the setting time and compressive strength, as shown in Table 1. The test materials used in the following examples, unless otherwise specified, were purchased from conventional stores and other channels. The quantitative tests in the following examples were all repeated three times, and the data are the average or average ± standard deviation of the three repeated experiments.

[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 cooperate 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 adding 10% of the 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 agent components are not stirred at a constant temperature of 80° C., the setting 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 calcium dodecaaluminate, 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 are only preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present application should be included in the protection scope of the present application. The above are only preferred implementation methods 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, and these improvements and variations should also be regarded as the protection scope of the present application.

Claims

1. A setting regulator for cement-clay two-component grouting material, characterized in that: The setting agent consists of dodecaluminate heptaaluminate, nano aluminum sol, aluminum sulfate, polyaluminum calcium chloride, N,N-dimethylethanolamine and diphenylmethane diisocyanate.

2. The setting agent according to claim 1, characterized in that The components in 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.

3. The method for preparing the setting regulator for cement-clay two-component grouting material according to any one of claims 1 to 2, characterized in that: include: 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; 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 regulator.

4. The method according to claim 3, characterized in that The preset temperature is 80°C.

5. The method according to claim 3, characterized in that: The first preset duration is 20 minutes.

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

7. The method according to claim 3, characterized in that The drying temperature of the drying is 40°C.

8. The method according to claim 3, characterized in that The third preset duration is 24 hours.

9. The use of the setting regulator for cement-clay two-component grouting material according to any one of claims 1 to 2, characterized in that: The setting regulator is applied to cement-clay two-component grouting material in which cement accounts for more than 40% of the total solid phase mass.

10. The use according to claim 9, 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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