Industrial waste residue mineralizer and preparation method thereof

Abstract

The invention relates to the technical field of cement preparation, and discloses an industrial waste residue mineralizer and a preparation method thereof.Industrial waste residues, water, triisopropanolamine, sodium sulfonate modified silane and sodium thiosulfate are added into a reactor and stirred, and the industrial waste residue mineralizer is obtained after stirring is finished. The preparation method comprises the following steps: carrying out reaction on chlorine in cyanuric chloride and amino in 3-dimethylamino-1-propylamine to obtain an intermediate, and carrying out addition reaction on silicon-hydrogen bonds in hexamethyldisilazane and alkenyl in allyl-1, 3-sultone to obtain tertiary amino silane; carrying out reaction on tertiary amino silane, tertiary amino in the intermediate and bromine in bromoethanol to obtain quaternized silane; the preparation method comprises the following steps: reacting amino in 1, 4-xylylenediamine with sultone in quaternized silane to obtain sodium sulfonate modified silane; the mineralizer contains a large amount of quaternary ammonium salt and sodium sulfonate and is applied to cement, the compressive strength of the cement is improved, the substitution degree of the quaternary ammonium salt is high, and the compressive strength of the cement is further improved.

Description

Technical Field

[0001] The invention relates to the technical field of cement preparation, in particular to an industrial waste slag mineralizer and a preparation method thereof. Background Art

[0002] Cement, also known as cement, red clay, etc., is a powdery hydraulic inorganic cementitious material that solidifies and hardens after mixing with water. It is usually not used alone, but is combined with sand and gravel to form mortar or concrete. It is widely used in civil engineering, water conservancy and other projects. In the prior art, cement mineralizers are generally added to cement during mixing to increase the reactivity of cement. For example, patent CN118405863A discloses a method for preparing and applying a special mineralizer for solid waste-based low-carbon cement clinker. The cement clinker produced by this invention is a high-iron phase low-carbon clinker. This type of low-carbon cement has low carbon emissions and strong corrosion resistance, but its compressive strength needs to be improved. Summary of the invention

[0003] 1. Technical issues to be resolved

[0004] In view of the deficiencies in the prior art, the present invention provides an industrial waste slag mineralizer and a preparation method thereof, which improves the compressive strength of cement.

[0005] (II) Technical solution

[0006] To achieve the above object, the present invention provides the following technical scheme: an industrial waste slag mineralizer and a preparation method thereof, comprising the following components by weight: 50-70 parts by weight of industrial waste slag, 6-18 parts by weight of water, 10-14 parts by weight of triisopropanolamine, 3-5 parts by weight of sodium sulfonate modified silane, and 1-2 parts by weight of sodium thiosulfate.

[0007] Preferably, the preparation method of the sodium sulfonate modified silane is:

[0008] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, adding a potassium carbonate aqueous solution with a molar concentration of 2-6 mol / L, reacting at a temperature of 35-60° C. for 4-12 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0009] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, heating to 60-80° C. and reacting for 8-10 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0010] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 3-5 minutes, and continuing to add bromoethanol, reacting at 65-80° C. for 6-12 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0011] (4) 1,4-phenylenediamine and quaternary ammonium silane are dissolved in a reaction solvent, and then a sodium hydroxide solution with a mass fraction of 3-6% is added dropwise, and the temperature is raised to 65-80° C. to react for 7-13 hours. After the reaction, the solvent is removed by dropwise vacuum concentration, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified silane.

[0012] Preferably, the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine in (1) is 1:1.3-1.6.

[0013] Preferably, the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst in (2) is 1.1-1.3:1:0.01-0.03.

[0014] Preferably, the mass ratio of tertiary aminosilane, intermediate and bromoethanol in (3) is 1:0.8-1.2:2.2-2.4.

[0015] Preferably, the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane in (4) is 1:1.2-1.4.

[0016] Preferably, the preparation method of the industrial waste slag mineralizer is: add industrial waste slag, water, triisopropanolamine, sodium sulfonate modified silane, and sodium thiosulfate into a reactor, stir for 4-10 minutes, and then obtain the industrial waste slag mineralizer.

[0017] (III) Beneficial technical effects

[0018] The invention provides an industrial waste residue mineralizer by adding industrial waste residue, water, triisopropanolamine, sodium sulfonate modified silane and sodium thiosulfate into a reactor and stirring the mixture.

[0019] The chlorine in cyanuric chloride reacts with the amino group in 3-dimethylamino-1-propylamine to introduce a tertiary amine group, thereby obtaining an intermediate, and the silicon-hydrogen bond in hexamethyldisilazane and the alkenyl group in allyl-1,3-sultone react to obtain a tertiary aminosilane; the tertiary aminosilane, the tertiary amino group in the intermediate and the bromine in bromoethanol react to obtain a quaternary ammonium silane; the amino group in 1,4-phenylenediamine reacts with the sultone in the quaternary ammonium silane to obtain a sodium sulfonate modified silane. The mineralizer contains a large amount of quaternary ammonium salt and sodium sulfonate, and its application in cement improves the compressive strength of cement, and the quaternary ammonium salt has a high degree of substitution, which further improves its compressive strength. DETAILED DESCRIPTION

[0020] Example 1

[0021] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, wherein the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine is 1:1.3, adding a potassium carbonate aqueous solution with a molar concentration of 2 mol / L, reacting at 35° C. for 4 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0022] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst is 1.1:1:0.01, heating to 60° C. and reacting for 8 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0023] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 3 minutes, and continuing to add bromoethanol, wherein the mass ratio of tertiary aminosilane, intermediate and bromoethanol is 1:0.8:2.2, reacting at 65° C. for 6 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0024] (4) dissolving 1,4-phenylenediamine and quaternary ammonium silane in a reaction solvent, wherein the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane is 1:1.2, then dropping a 3% sodium hydroxide solution, heating to 65° C. for reaction for 7 h, dropping and concentrating under reduced pressure after the reaction to remove the solvent, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified silane;

[0025] (5) 50 parts by weight of industrial waste slag, 6 parts by weight of water, 10 parts by weight of triisopropanolamine, 3 parts by weight of sodium sulfonate-modified silane, and 1 part by weight of sodium thiosulfate were added into a reactor and stirred for 4 minutes to obtain an industrial waste slag mineralizer.

[0026] Example 2

[0027] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, wherein the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine is 1:1.6, adding a potassium carbonate aqueous solution with a molar concentration of 6 mol / L, reacting at a temperature of 60° C. for 12 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0028] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst is 1.3:1:0.03, heating to 80° C. and reacting for 10 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0029] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 5 minutes, and continuing to add bromoethanol, wherein the mass ratio of tertiary aminosilane, intermediate and bromoethanol is 1:1.2:2.4, reacting at 80° C. for 12 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0030] (4) dissolving 1,4-phenylenediamine and quaternary ammonium silane in a reaction solvent, wherein the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane is 1:1.4, then dropping a 6% sodium hydroxide solution, heating to 80° C. to react for 13 h, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified silane;

[0031] (5) 70 parts by weight of industrial waste slag, 18 parts by weight of water, 14 parts by weight of triisopropanolamine, 5 parts by weight of sodium sulfonate-modified silane, and 2 parts by weight of sodium thiosulfate were added into a reactor and stirred for 10 minutes to obtain an industrial waste slag mineralizer.

[0032] Example 3

[0033] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, wherein the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine is 1:1.4, adding a potassium carbonate aqueous solution with a molar concentration of 4 mol / L, reacting at 47° C. for 8 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0034] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst is 1.2:1:0.02, heating to 70° C. and reacting for 9 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0035] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 4 minutes, and continuing to add bromoethanol, wherein the mass ratio of tertiary aminosilane, intermediate and bromoethanol is 1:1:2.3, reacting at 72° C. for 9 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0036] (4) dissolving 1,4-phenylenediamine and quaternary ammonium silane in a reaction solvent, wherein the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane is 1:1.3, then dropping a 4% sodium hydroxide solution, heating to 72° C. to react for 10 h, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium sulfonate modified silane;

[0037] (5) 60 parts by weight of industrial waste slag, 11 parts by weight of water, 12 parts by weight of triisopropanolamine, 4 parts by weight of sodium sulfonate-modified silane, and 1.5 parts by weight of sodium thiosulfate were added into a reactor and stirred for 7 minutes to obtain an industrial waste slag mineralizer.

[0038] Example 4

[0039] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, wherein the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine is 1:1.3, adding a potassium carbonate aqueous solution with a molar concentration of 2 mol / L, reacting at 35° C. for 4 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0040] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst is 1.1:1:0.01, heating to 60° C. and reacting for 8 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0041] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 5 minutes, and continuing to add bromoethanol, wherein the mass ratio of tertiary aminosilane, intermediate and bromoethanol is 1:1.2:2.4, reacting at 80° C. for 12 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0042] (4) dissolving 1,4-phenylenediamine and quaternary ammonium silane in a reaction solvent, wherein the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane is 1:1.4, then dropping a 6% sodium hydroxide solution, heating to 80° C. to react for 13 h, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified silane;

[0043] (5) 60 parts by weight of industrial waste slag, 11 parts by weight of water, 12 parts by weight of triisopropanolamine, 4 parts by weight of sodium sulfonate-modified silane, and 1.5 parts by weight of sodium thiosulfate were added into a reactor and stirred for 7 minutes to obtain an industrial waste slag mineralizer.

[0044] Example 5

[0045] (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, wherein the mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine is 1:1.6, adding a potassium carbonate aqueous solution with a molar concentration of 6 mol / L, reacting at a temperature of 60° C. for 12 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate;

[0046] (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, wherein the mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst is 1.3:1:0.03, heating to 80° C. and reacting for 10 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane;

[0047] (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 4 minutes, and continuing to add bromoethanol, wherein the mass ratio of tertiary aminosilane, intermediate and bromoethanol is 1:1:2.3, reacting at 72° C. for 9 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane;

[0048] (4) dissolving 1,4-phenylenediamine and quaternary ammonium silane in a reaction solvent, wherein the mass ratio of 1,4-phenylenediamine to quaternary ammonium silane is 1:1.3, then dropping a 4% sodium hydroxide solution, heating to 72° C. to react for 10 h, dropping and concentrating under reduced pressure to remove the solvent after the reaction, and recrystallizing the crude product in ethanol to obtain sodium sulfonate modified silane;

[0049] (5) 50 parts by weight of industrial waste slag, 6 parts by weight of water, 10 parts by weight of triisopropanolamine, 3 parts by weight of sodium sulfonate-modified silane, and 1 part by weight of sodium thiosulfate were added into a reactor and stirred for 4 minutes to obtain an industrial waste slag mineralizer.

[0050] Comparative Example 1

[0051] 50 parts by weight of industrial waste slag, 6 parts by weight of water, 10 parts by weight of triisopropanolamine and 1 part by weight of sodium thiosulfate were added into a reactor and stirred for 4 minutes to obtain an industrial waste slag mineralizer.

[0052] Performance Testing

[0053] 35g of steel slag, 20g of limestone powder, 35g of fly ash and 2g of industrial waste slag mineralizer were added into the reactor and stirred evenly. After standing for 3 days, a cement product was obtained.

[0054] The industrial waste slag mineralizers of the embodiments and comparative examples were used to prepare cement products. The compressive strength was tested according to the national standard GB / T1761. The test results are shown in Table 1.

[0055] Table 1: Compressive strength test.

[0056]

[0057]

[0058] It can be seen from Table 1 that Examples 1-5 of the present invention have better compressive strength than Comparative Example 1.

[0059] The specific surface area of ​​the material was tested according to GB / T8074-2008 "Determination of specific surface area of ​​cement - Blaine method", and the test results are shown in Table 2.

[0060] Table 2: Specific surface area test.

[0061] project <![CDATA[Specific surface area (m 2 / kg)]]> in conclusion Example 1 310 qualified Example 2 315 qualified Example 3 314 qualified Example 4 312 qualified Example 5 311 qualified Comparative Example 1 287 Failure

[0062] It can be seen from Table 2 that Examples 1-5 of the present invention have better specific surface areas than Comparative Example 1.

Claims

1. An industrial waste slag mineralizer, characterized in that: The invention comprises the following components by weight: 50-70 parts by weight of industrial waste residue, 6-18 parts by weight of water, 10-14 parts by weight of triisopropanolamine, 3-5 parts by weight of sodium sulfonate modified silane and 1-2 parts by weight of sodium thiosulfate.

2. The industrial waste slag mineralizer according to claim 1, characterized in that: The preparation method of the sodium sulfonate modified silane is: (1) adding 1,4-dioxane solvent, cyanuric chloride and 3-dimethylamino-1-propylamine to a reactor, adding a potassium carbonate aqueous solution with a molar concentration of 2-6 mol / L, reacting at a temperature of 35-60° C. for 4-12 hours, concentrating to remove the solvent after the reaction, then adding ethyl acetate for extraction, drying the organic phase with anhydrous magnesium sulfate to remove water, concentrating the filtrate, washing with ether, and then recrystallizing with ethanol to obtain an intermediate; (2) adding hexamethyldisilazane and propenyl-1,3-sultone to N,N-dimethylformamide solvent, stirring and dispersing, and then continuing to add chloroplatinic acid catalyst, heating to 60-80° C. and reacting for 8-10 hours, and then performing reduced pressure distillation after completion, washing and drying to obtain tertiary aminosilane; (3) adding the tertiary aminosilane and the intermediate to N,N-dimethylformamide solvent, stirring and mixing, stirring for 3-5 minutes, and continuing to add bromoethanol, reacting at 65-80° C. for 6-12 hours, and then rotary distilling and washing with petroleum ether to obtain quaternary ammonium silane; (4) 1,4-phenylenediamine and quaternary ammonium silane are dissolved in a reaction solvent, and then a sodium hydroxide solution with a mass fraction of 3-6% is added dropwise, and the temperature is raised to 65-80° C. to react for 7-13 hours. After the reaction, the solvent is removed by dropwise vacuum concentration, and the crude product is recrystallized in ethanol to obtain sodium sulfonate modified silane.

3. The industrial waste slag mineralizer according to claim 1, characterized in that: The mass ratio of cyanuric chloride to 3-dimethylamino-1-propylamine in (1) is 1:1.3-1.

6.

4. The industrial waste slag mineralizer according to claim 1, characterized in that: The mass ratio of hexamethyldisilazane, propenyl-1,3-sultone and chloroplatinic acid catalyst in (2) is 1.1-1.3:1:0.01-0.

03.

5. The industrial waste slag mineralizer according to claim 1, characterized in that: The mass ratio of tertiary aminosilane, intermediate and bromoethanol in (3) is 1:0.8-1.2:2.2-2.

4.

6. The industrial waste slag mineralizer according to claim 1, characterized in that: The mass ratio of 1,4-phenylenediamine to quaternary ammonium silane in (4) is 1:1.2-1.

4.

7. A method for preparing an industrial waste slag mineralizer according to any one of claims 1 to 6, characterized in that: The preparation method of the industrial waste slag mineralizer is as follows: industrial waste slag, water, triisopropanolamine, sodium sulfonate modified silane and sodium thiosulfate are added into a reactor, and stirred for 4-10 minutes, and then the industrial waste slag mineralizer is obtained.

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