A grouting material with controllable curing duration, its preparation method and application

Abstract

The present invention provides a grouting material with controllable curing duration, its preparation method and application. The grouting material is characterized in that it comprises a powder, a curing agent and a binder, and the mass ratio of the three is (58 - 80):(20 - 42):(0.01 - 8) in sequence. Among them, the powder comprises the following components in parts by mass: 0 - 30 parts of high alumina powder, 1 - 35 parts of fireclay, 1 - 75 parts of fly ash, 0 - 8 parts of calcined kaolin, 0.5 - 2 parts of borax, 8 - 15 parts of silicon carbide, 0.1 - 1.2 parts of lithium oxide, 8 - 15 parts of cement, 8 - 15 parts of silica fume, 0.01 - 1.5 parts of water reducing agent, 0.1 - 2 parts of explosion-proof fiber, and 0.01 - 0.08 parts of bleeding agent. The grouting material described in the present invention can adjust the initial setting duration of the grouting material within 0.5h - 48h according to the construction requirements, and enter the final setting within 3h - 168h.

Description

Technical Field

[0001] The present invention belongs to the field of refractory materials, and in particular relates to a grouting material with controllable curing time, a preparation method thereof and an application thereof. Background Art

[0002] The grouting material is prepared by using high-strength materials as aggregates, cement as a binder, and supplemented with substances such as high fluidity, micro-expansion, and anti-segregation. It can be used after adding a certain amount of water at the construction site and stirring evenly. The grouting material has the characteristics of good self-flowability, fast hardening, early strength, high strength, no shrinkage, and micro-expansion, and has the advantages of reliable quality, cost reduction, short construction period, and convenient use in construction. However, in the use process, it also has some limitations. The curing time is too short, which limits the fullness of the grouting fluidity and is not suitable as a grouting material for blast furnace repair.

[0003] The publication number CN104230275A discloses a high-strength non-shrinking building grouting material, with main raw materials such as 35 parts of portland cement, 25 parts of foundry waste sand, 1.5 parts of zinc dialkyldithiophosphate, 3.5 parts of guar gum, etc. The formula of this application is suitable for grouting of normal-temperature buildings, but its early strength time is short, and the slurry transportation and storage are relatively difficult. The publication number CN116143483A discloses a preparation method of a cement-based grouting material, which is mainly prepared by using calcium carbonate, fly ash, bentonite and other auxiliary materials to prepare a grouting material for normal-temperature use. Its curing time is slow and it cannot meet the operation requirements of short-time kiln repair.

[0004] At present, there is less research on the basic materials of slurry for normal-temperature curing of the furnace wall of industrial kilns, and there are even fewer products with controllable slurry curing time under normal-temperature use conditions. Therefore, in view of the demand for controllable curing time of grouting materials for industrial kilns, a grouting material with controllable curing time is developed, and the grouting material has certain mechanical strength after curing. Summary of the Invention

[0005] In view of this, the present invention aims to overcome the defects in the prior art and provides a grouting material with controllable curing time, a preparation method thereof and an application thereof.

[0006] To achieve the above object, the technical solution of the present invention is realized as follows:

[0007] In the first aspect, the present invention provides a grouting material with controllable curing time, which includes powder, binder, curing agent and pH regulator. Among them, the mass ratio of the powder to the binder is (58 - 80):(20 - 42), the addition amount of the curing agent is 1% - 6% of the mass of the powder, and the pH regulator adjusts the pH value of the grouting material to 4 - 9; the powder includes the following components in parts by mass:

[0008] 0 - 30 parts of high - alumina powder, 1 - 35 parts of fireclay, 1 - 75 parts of fly ash, 0 - 8 parts of calcined kaolin, 0.5 - 2 parts of borax, 8 - 15 parts of silicon carbide, 0.1 - 1.2 parts of lithium oxide, 8 - 15 parts of cement, 8 - 15 parts of silica fume, 0.01 - 1.5 parts of water - reducing agent, 0.1 - 2 parts of explosion - proof fiber, 0.01 - 0.08 parts of bleeding agent.

[0009] Preferably, the curing agent is a rare - earth chloride solution.

[0010] Preferably, the pH regulator is one or more of citric acid, tartaric acid, sodium hydroxide, and ammonia water.

[0011] More preferably, the rare - earth chloride is one or more of lanthanum chloride, cerium chloride, lanthanum - cerium chloride, lanthanum - samarium chloride, samarium chloride, and yttrium chloride.

[0012] Further preferably, the preparation method of the rare - earth chloride includes the following steps:

[0013] Take an acid solution and place it in a high - temperature reactor, stir and heat it to 65 - 85 °C. Add rare - earth materials in batches, adjust the pH value of the solution to 6 - 7 until the solution is completely clear. Take out the solution for filtration to remove insoluble impurities. Add the filtered solution back to the high - temperature reactor, stir and heat it to 125 °C - 150 °C. After crystallization appears in the solution, adjust the stirring speed to 1 - 60 rpm. Turn off the heating, and after cooling to room temperature, perform suction filtration on the crystallization solution. Filter out all the crystals, and add pure water to adjust the concentration to 1 - 5 g / ml to obtain the rare - earth chloride solution.

[0014] Preferably, the acid solution is hydrochloric acid, and the concentration of the hydrochloric acid is 18 - 19 wt%; the rare - earth material is rare - earth oxide or rare - earth carbonate, the addition amount of the acid solution is 50 - 100 parts, and the addition amount of the rare - earth material is 50 - 100 parts.

[0015] Preferably, the binder is one or more of sodium silicate, silica sol, aluminum sol, zirconium sol, aluminum dihydrogen phosphate, phenolic resin, hydroxymethylphenol, amino silicone resin, methyl polysiloxane, imidazole epoxy resin, acrylic resin, aluminum hydrogen phosphate, organohalosilane polymer, diethylenetriamine, trimethylhexamethylenediamine, 1,2 - diamino - cyclohexane, methylenebis(cyclohexylamine), trimethylhexamethylenediamine.

[0016] Preferably, the particle size of the fly ash is 1200 - 1800 mesh.

[0017] The present invention also provides a preparation method of the grouting material with controllable curing time, including the following steps:

[0018] Add the powder into a three-dimensional powder mixer and mix it thoroughly. Transfer the uniformly mixed powder into a cement mortar mixer, stir at a low speed for 0.5 - 1 h, then add the binder and stir at a high speed for 0.1 - 0.5 h. Add the curing agent and pH regulator, and then stir at a high speed for 0.01 - 48 h.

[0019] Due to their special outermost electron structures, rare earth elements can not only oxidize or combine with antioxidants in the binder to form complex precipitates through their own valence changes in the prepared rare earth chloride solution, but also form coordination bonds with polar groups such as hydroxyl groups and hydroxymethyl groups in resins such as alkyd, phenolic, amino, and epoxy through their empty orbitals, increasing the crosslinking degree of the molecular structure and generating coordination complexes with larger relative molecular masses, thereby accelerating the curing reaction of the binder. At the same time, the added pH regulator can adjust the acidity and alkalinity of the grouting material system in the mixed system, affect the polycondensation reaction of phenolic resin, and inhibit or promote the complexation reaction of rare earth ions, thus making the curing time of the grouting material controllable.

[0020] The present invention also provides the application of the above grouting material with controllable curing time as a normal temperature curing slurry for the furnace wall of industrial kilns.

[0021] Compared with the prior art, the present invention has the following advantages:

[0022] (1) The initial setting time of the grouting material of the present invention can be adjusted within 0.5 h - 48 h according to construction requirements, and the final setting occurs within 3 h - 168 h. In the prior art, the initial setting generally occurs within 3 h for grouting, the slurry loses fluidity, and the final setting occurs within 3 h - 8 h for complete curing, which cannot meet the working requirements with a longer construction duration.

[0023] (2) After curing, the thermal conductivity of the grouting material of the present invention decreases by more than 17% compared with that of conventional grouting materials, and it has stronger heat insulation.

[0024] (3) The flexural strength of the grouting material of the present invention is increased by more than 20% compared with that of conventional grouting materials, and the compressive strength is increased by 10% with higher advantages.

[0025] (4) The linear change rate of the grouting material of the present invention is reduced by more than 50%. Detailed implementation mode

[0026] Unless otherwise defined, the technical terms used in the following examples have the same meanings as commonly understood by those skilled in the technical field to which the present invention pertains. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0027] The following examples are used to illustrate the present invention in detail.

[0028] Example 1

[0029] Take 700 g of powder (21 parts of high-aluminum powder, 33 parts of fireclay, 10 parts of fly ash, 5 parts of calcined kaolin, 1 part of borax, 12 parts of silicon carbide, 1 part of lithium oxide, 5.8 parts of cement, 10 parts of silica fume, 0.05 part of water reducer, 0.1 part of explosion-proof fiber, 0.05 part of bleeding agent), mix well, then add 300 g of phenolic resin and mix evenly. Add 12 ml of lanthanum cerium chloride solution (3 g / ml), add tartaric acid to make the pH value of the grouting material 6.0, and mix evenly again. Pour the grouting material into a standard castable specimen mold (40*40*160 mm). Initial setting occurs after 1 h, and final setting occurs after 12 h. Then remove the sample bar for testing, and the results are shown in Table 1.

[0030] Example 2

[0031] Take 700 g of powder (21 parts of high-aluminum powder, 33 parts of fireclay, 10 parts of fly ash, 5 parts of calcined kaolin, 1 part of borax, 12 parts of silicon carbide, 1 part of lithium oxide, 5.8 parts of cement, 10 parts of silica fume, 0.05 part of water reducer, 0.1 part of explosion-proof fiber, 0.05 part of bleeding agent), mix well, then add 300 g of phenolic resin and mix evenly. Add 10 ml of cerium chloride solution (1.5 g / ml), add citric acid to make the pH value of the grouting material about 6.5, and mix evenly again. Pour the grouting material into a standard castable specimen mold (40*40*160 mm). Initial setting occurs after 12 h, and final setting occurs after 36 h. Then remove the sample bar for testing, and the results are shown in Table 1.

[0032] Example 3

[0033] Take 700 g of powder (21 parts of high-aluminum powder, 33 parts of fireclay, 10 parts of fly ash, 5 parts of calcined kaolin, 1 part of borax, 12 parts of silicon carbide, 1 part of lithium oxide, 5.8 parts of cement, 10 parts of silica fume, 0.05 part of water reducer, 0.1 part of explosion-proof fiber, 0.05 part of bleeding agent), mix well, then add 300 g of phenolic resin and mix evenly. Then add 1.03 ml of yttrium chloride solution (2.5 g / ml), add ammonia water to make the pH value of the grouting material about 8.0, and mix evenly again. Pour the grouting material into a standard castable specimen mold (40*40*160 mm). Initial setting occurs after 48 h, and final setting occurs after 128 h. Then remove the sample bar for testing, and the results are shown in Table 1.

[0034] Example 4

[0035] The preparation process of the grouting material in this example is the same as that in Example 1, except that: the mass of the powder is 580 g, the mass of the phenolic resin is 420 g, 5.8 ml of lanthanum cerium chloride solution (1 g / ml), and add sodium hydroxide to make the pH value of the grouting material about 9. The test results of the sample bar are shown in Table 1.

[0036] Example 5

[0037] The preparation process of the grouting material of this embodiment is the same as that of embodiment 1, except that: the mass of the powder is 800 g, the mass of the phenolic resin is 200 g, the lanthanum cerium chloride solution (1 g / ml) is 48 ml, and sodium hydroxide is added to make the pH value of the grouting material about 4. The test results of the sample strips are shown in Table 1.

[0038] Comparative Example 1

[0039] Take 700g of powder (21 parts of high aluminum powder, 33 parts of coke gemstone, 10 parts of fly ash, 5 parts of calcined kaolin, 1 part of borax, 12 parts of silicon carbide, 1 part of lithium oxide, 5.8 parts of cement, 10 parts of silicon micropowder, 0.05 parts of water reducer, 0.1 parts of explosion-proof fiber, 0.05 parts of water bleeding agent), mix thoroughly, add 300g of phenolic resin, mix evenly, and pour into the standard casting material sample mold (40*40*160mm). The grouting material does not solidify.

[0040] Comparative Example 2

[0041] The preparation process of the grouting material of this comparative example is the same as that of Example 1, except that no lanthanum cerium chloride solution is added. The grouting material does not solidify.

[0042] Comparative Example 3

[0043] The preparation process of the grouting material of this comparative example is the same as that of Example 1, except that no sodium hydroxide is added. The test results of the sample strips are shown in Table 1.

[0044] Comparative Example 4

[0045] The preparation process of the grouting material of this comparative example is the same as that of Example 1, except that: 49 ml of lanthanum chloride cerium solution (1 g / ml) was used. The grouting material solidified too quickly and solidified during the stirring process, so it was impossible to prepare a sample block for testing.

[0046] Table 1: Grouting material performance data table

[0047]

[0048] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A grouting material with controllable curing duration, characterized in that: It includes powder, binder, curing agent and pH regulator. Among them, the mass ratio of the powder to the binder is (58 - 80):(20 - 42), the addition amount of the curing agent is 1% - 6% of the mass of the powder, and the pH regulator adjusts the pH value of the grouting material to 4 - 9; the powder includes the following components in parts by mass: 0 - 30 parts of high alumina powder, 1 - 35 parts of pyrophyllite, 1 - 75 parts of fly ash, 0 - 8 parts of calcined kaolin, 0.5 - 2 parts of borax, 8 - 15 parts of silicon carbide, 0.1 - 1.2 parts of lithium oxide, 8 - 15 parts of cement, 8 - 15 parts of silica fume, 0.01 - 1.5 parts of water reducing agent, 0.1 - 2 parts of explosion - proof fiber, 0.01 - 0.08 parts of bleeding agent; The curing agent is a rare earth chloride solution; The binder is one or more of water glass, silica sol, aluminum sol, zirconium sol, aluminum dihydrogen phosphate, phenolic resin, hydroxymethylphenol, amino silicone resin, methyl polysiloxane, imidazole epoxy resin, acrylic resin, aluminum hydrogen phosphate, organohalosilane polymer, diethylenetriamine, trimethylhexamethylenediamine, 1,2 - diaminocyclohexane, methylenebiscyclohexylamine, trimethylhexamethylenediamine; 2. The grouting material with controllable curing duration according to claim 1, wherein: The pH regulator is one or more of citric acid, tartaric acid, sodium hydroxide, ammonia water; 3. The grouting material with controllable curing duration according to claim 1, characterized in that: The rare earth chloride is one or more of lanthanum chloride, cerium chloride, lanthanum cerium chloride, lanthanum samarium chloride, samarium chloride, yttrium chloride; 4. The grouting material with controllable curing duration according to claim 1, characterized in that: The preparation method of the curing agent includes the following steps: Put the acid solution into a high - temperature reaction kettle, stir and heat it to 65 - 85 °C, add the rare earth material in batches, adjust the pH value of the solution to 6 - 7 until the solution is completely clear, take out the solution for filtration, filter out the insoluble impurities, add the filtered solution back into the high - temperature reaction kettle, stir and heat it again to 125 °C - 150 °C. After crystallization appears in the solution, adjust the stirring speed to 1 - 60 rpm, turn off the heating, and after cooling to room temperature, perform suction filtration on the crystallization solution, filter out all the crystals, and add pure water to adjust the concentration to 1 - 5 g / ml to obtain the rare earth chloride solution.

5. The grouting material with controllable curing duration according to claim 4, characterized in that: The acid solution is hydrochloric acid, and the concentration of the hydrochloric acid is 18 - 19 wt%; the rare earth material is rare earth oxide or rare earth carbonate, the addition amount of the acid solution is 50 - 100 parts, and the addition amount of the rare earth material is 50 - 100 parts.

6. The grouting material with controllable curing duration according to claim 1, characterized in that: The particle size of the fly ash is 1200 - 1800 mesh.

7. The preparation method of the grouting material with controllable curing duration according to any one of claims 1-6, characterized in that: It includes the following steps: Put the powder into a three - dimensional powder mixer and mix it evenly. Transfer the evenly mixed powder into a cement mortar mixer, stir at low speed for 0.5 - 1 h, then add the binder, stir at high speed for 0.1 h - 0.5 h, add the curing agent and pH regulator, and then stir at high speed for 0.01 h - 48 h.

8. Application of the grouting material with controllable curing time as claimed in any one of claims 1 - 6 in the industrial kiln furnace wall curing slurry.

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