Cement raw material additive and preparation method thereof

Abstract

The invention belongs to the technical field of cement production, and particularly relates to a cement raw material additive and a preparation method thereof.The cement raw material additive contains, by weight, 0.1%-5% of hydroxyl carboxylate, 0.5%-5% of sugar manufacturing waste liquid and 0.5%-5% of saponification waste alkali liquor, the hydroxyl carboxylate accounts for 0.1%-5% of the cement raw material additive, and the saponification waste alkali liquor accounts for 0.5%-5% of the cement raw material additive. The weight of the saponification waste alkali liquid accounts for 90-98% of the weight of the cement raw material additive; wherein the saponification waste alkali liquor contains water accounting for 45-75% of the weight of the saponification waste alkali liquor, organic acid sodium salt accounting for 5-25% of the weight of the saponification waste alkali liquor and sodium hydroxide accounting for 5.5-6.5% of the weight of the saponification waste alkali liquor. According to the invention, by simultaneously adding the hydroxy carboxylate, the sugar production waste liquid and the saponification waste alkali liquid, waste can be turned into wealth, a good grinding aiding effect can be generated, the material fluidity in the grinding process can be improved, 80-micron screen residues can be reduced, the grindability and burnability of the raw material can be improved, and the strength of the cement clinker can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of cement production, and in particular to a cement raw material additive and a preparation method thereof. Background Art

[0002] Research and development of cement raw material additives can improve the fluidity, dispersibility and grindability of materials, reduce grinding energy consumption, increase the processing volume and fineness compliance rate of raw materials per unit time, thereby improving the overall grinding efficiency; it can help adjust the particle grading of raw materials, make the clinker mineral composition more uniform, and facilitate the full reaction of minerals such as C3S and C2S in the subsequent firing process, thereby improving the strength and durability of cement products. In addition, cement raw material additives can also reduce coal consumption, reduce coal-burning pollution and protect the environment. Research and development of cement raw material additives is also conducive to improving the quality and market competitiveness of corporate products.

[0003] Cement raw material grinding is a necessary process and key link in cement production. In the process of cement raw material grinding, in order to improve raw material quality control, prevent material blockage and segregation, improve grinding efficiency and optimize particle grading, as well as save energy and reduce emissions, domestic cement companies generally take two measures: one is to improve the structure of grinding machinery, improve the grinding process and method so that more mechanical energy can act on the material through the grinding medium; the other method is to add trace or small amounts of additives, namely grinding aids, during the grinding process to affect the mechanical and chemical processes in the crushing operation, so as to achieve the purpose of improving grinding efficiency. Cement raw material grinding aids adsorb on the surface of cement particles, reduce the surface energy of the particles or cause the position migration of the crystal lattice near the surface layer, produce point or line defects, thereby reducing the strength and hardness of the particles. This helps to speed up the grinding speed of the material and improve the grinding efficiency. It can also improve the fluidity and dispersibility of the material, reduce the blockage and segregation of the material during the batching and grinding process, ensure that the raw materials can enter the mill in the expected proportion, and stabilize the composition of the raw material out of the mill. The application of raw material grinding aids can optimize the particle size distribution of raw materials, improve the grindability and burnability of raw materials, and has the advantages of quick effect and simple operation, so it is increasingly valued. The additive components used are generally polymer compounds, but waste materials are rarely used as additive components. Summary of the invention

[0004] In view of the above problems, the present invention provides a cement raw material additive and a preparation method thereof. The present invention simultaneously adds hydroxycarboxylate, sugar production waste liquid and saponification waste alkali liquid into the cement raw material additive, which can not only turn waste into treasure, but also produce a good grinding aid effect, can improve the material fluidity during the grinding process, reduce the 80-micron sieve residue, and can optimize the particle size distribution of the raw material, improve the grindability and burnability of the raw material, and improve the strength of the cement clinker.

[0005] To achieve the above purpose, the technical solution adopted by the present invention is as follows:

[0006] A cement raw material additive, which contains hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor, wherein the weight of the hydroxycarboxylate accounts for 0.1-5% of the weight of the cement raw material additive, the weight of the sugar waste liquor accounts for 0.5-5% of the weight of the cement raw material additive, and the weight of the saponification waste alkali liquor accounts for 90-98% of the weight of the cement raw material additive; the saponification waste alkali liquor contains water accounting for 45-75% of the weight of the saponification waste alkali liquor, organic acid sodium salt accounting for 5-25% of the weight of the saponification waste alkali liquor, and sodium hydroxide accounting for 5.5-6.5% of the weight of the saponification waste alkali liquor.

[0007] Preferably, the waste alkali solution from saponification is the waste alkali solution from saponification produced during the production of cyclohexanone by air oxidation of cyclohexane.

[0008] Preferably, the pH of the saponification waste alkali solution is ≥13, and the solid content is ≥32% (wt).

[0009] Preferably, the cement raw material additive further contains tartaric acid, and the weight of the tartaric acid accounts for 1-1.5% of the weight of the cement raw material additive.

[0010] Preferably, the hydroxycarboxylate is sodium gluconate, sodium citrate or sodium tartrate.

[0011] Preferably, the cement raw material additive further contains a defoamer, the weight of the defoamer accounts for 0.1-1% of the weight of the cement raw material additive, and the defoamer includes an organosilicon defoamer and / or a polyether modified silicon additive.

[0012] Preferably, the cement raw material additive further contains a cement accelerator, the weight of the cement accelerator accounts for 0.1-1% of the weight of the cement raw material additive, and the cement accelerator includes at least one of triisopropanolamine, triethanolamine, ethylene glycol, polyethylene glycol and calcium hydroxide.

[0013] Further preferably, the polyethylene glycol is a low molecular weight polyethylene glycol.

[0014] The present invention also provides a method for preparing a cement raw material additive, which comprises mixing and stirring 0.1-5 parts of hydroxycarboxylate, 0.5-5 parts of sugar waste liquid, 90-98 parts of saponification waste alkali liquid, 1-1.5 parts of tartaric acid, 0.1-1 parts of defoaming agent and 0.1-1 parts of cement accelerator by weight for reaction, and the reaction time is 4-5 hours.

[0015] By adopting the above technical solution, the beneficial effects of the present invention are:

[0016] The present invention adds hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor to the cement raw material additive at the same time, wherein the hydroxycarboxylate can be used as a retarder and has a good dispersing effect. The main substances in the sugar waste liquor are sugar residue, organic matter and sugar, which can be used as a cement reinforcing agent to improve the compression and flexural strength of cement. However, since the sugar residue and the like are in an agglomerated state in the sugar waste liquor, the hydroxycarboxylate with a dispersing effect can be used to fully disperse the sugar residue in the sugar waste liquor, so that the grinding aid effect is better; and the hydroxycarboxylate can remove the grease in the sugar waste liquor through adsorption and chemical reaction, so that the sugar waste liquor has a better grinding aid effect; and the organic acid sodium salt in the saponification waste alkali liquor activates the activity of the calcium carbonate lattice in the form of a solid solution, plays a cement raw material grinding aid effect, and can also improve the material fluidity during the grinding process. The addition of the sugar waste liquor can also avoid the reduction of friction between materials due to excessive addition of saponification waste alkali liquor, so that effective grinding cannot be obtained.

[0017] Therefore, the present invention simultaneously adds hydroxycarboxylate, sugar production waste liquid and saponification waste alkali liquid into the cement raw material additive, which can not only turn waste into treasure, but also produce a good grinding aid effect, can improve the material fluidity during the grinding process, reduce the 80-micron sieve residue, and can optimize the particle size distribution of the raw material, improve the grindability and burnability of the raw material, and improve the strength of the cement clinker. DETAILED DESCRIPTION

[0018] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] Example 1

[0020] A cement raw material additive, which contains hydroxycarboxylate, sugar waste liquor, saponified waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane, and tartaric acid. The weight of hydroxycarboxylate accounts for 1.5% of the weight of the cement raw material additive, the weight of sugar waste liquor accounts for 2.5% of the weight of the cement raw material additive, the weight of saponified waste alkali liquor accounts for 95% of the weight of the cement raw material additive, and the weight of tartaric acid accounts for 1% of the weight of the cement raw material additive.

[0021] The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane has a pH value of ≥13 and a solid content of ≥32% (wt). The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane mainly includes the following components in percentage by weight: 20% (wt) of organic acid sodium salt; 1.5% (wt) of sodium carbonate; 5.5% (wt) of sodium hydroxide; and 73% (wt) of water.

[0022] Tartaric acid and the like react with sodium carbonate and sodium hydroxide in the saponification waste alkali solution to increase the concentration of organic acid sodium salt in the grinding aid, thereby improving the grinding aid effect and playing a good grinding aid role.

[0023] The hydroxycarboxylate in the present invention can be selected from sodium gluconate, sodium citrate or sodium tartrate. In this embodiment, sodium gluconate is preferred, so that the oil in the sugar waste liquid can be removed by adsorption and chemical reaction, so that the sugar waste liquid has a better grinding aid effect.

[0024] The present invention provides a method for preparing a cement raw material additive, which comprises mixing 1.5 parts of hydroxycarboxylate, 2.5 parts of sugar waste liquid, 95 parts of saponification waste alkali liquid and 0.95 parts of tartaric acid by weight, stirring and reacting for 5 hours. After the reaction is completed, the cement raw material additive of the present embodiment is obtained.

[0025] Example 2

[0026] A cement raw material additive, which contains hydroxycarboxylate, sugar waste liquor, saponified waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane, tartaric acid and cement accelerator. Among them, the weight of hydroxycarboxylate accounts for 2% of the weight of the cement raw material additive, the weight of sugar waste liquor accounts for 3% of the weight of the cement raw material additive, the weight of saponified waste alkali liquor accounts for 93% of the weight of the cement raw material additive, the weight of the cement accelerator accounts for 0.5% of the weight of the cement raw material additive, and the weight of tartaric acid accounts for 1.5% of the weight of the cement raw material additive.

[0027] The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane has a pH value of ≥13 and a solid content of ≥32% (wt). The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane mainly includes the following components in percentage by weight: 20% (wt) of organic acid sodium salt; 1.5% (wt) of sodium carbonate; 5.5% (wt) of hydroxide; and 73% (wt) of water.

[0028] Tartaric acid reacts with sodium carbonate and sodium hydroxide in the saponification waste alkali solution to increase the concentration of organic acid sodium salt in the grinding aid, thereby improving the grinding aid effect and playing a good grinding aid role.

[0029] The hydroxycarboxylate in the present invention can be selected from sodium gluconate, sodium citrate or sodium tartrate. In this embodiment, sodium citrate is preferred, so that sodium citrate can be used to remove oil from the sugar waste liquid through adsorption and chemical reaction, so that the sugar waste liquid has a better grinding aid effect.

[0030] In the present invention, the cement accelerator can be selected from at least one of triisopropanolamine, triethanolamine, ethylene glycol, polyethylene glycol and calcium hydroxide. Wherein, polyethylene glycol is a low molecular weight polyethylene glycol. In this embodiment, a solution obtained by mixing triethanolamine and polyethylene glycol in a ratio of 1:1 is preferably used as the cement accelerator in the cement raw material additive.

[0031] The present invention provides a method for preparing a cement raw material additive, specifically comprising mixing and stirring 2 parts of hydroxycarboxylate, 3 parts of sugar waste liquid, 93 parts of saponification waste alkali liquid, 1.5 parts of tartaric acid and 0.5 parts of cement accelerator by weight for 4 hours. After the reaction is completed, the cement raw material additive of the present embodiment is obtained.

[0032] Example 3

[0033] A cement raw material additive, which contains hydroxycarboxylate, sugar waste liquor, saponified waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane, tartaric acid, defoamer and cement accelerator. Among them, the weight of hydroxycarboxylate accounts for 2.8% of the weight of the cement raw material additive, the weight of sugar waste liquor accounts for 3% of the weight of the cement raw material additive, the weight of saponified waste alkali liquor accounts for 92% of the weight of the cement raw material additive, the weight of defoamer accounts for 0.5% of the weight of the cement raw material additive, the weight of cement accelerator accounts for 0.5% of the weight of the cement raw material additive, and the weight of tartaric acid accounts for 1.2% of the weight of the cement raw material additive.

[0034] The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane has a pH value of ≥13 and a solid content of ≥32% (wt). The saponification waste alkali liquor produced in the process of producing cyclohexanone by air oxidation of cyclohexane mainly includes the following components in percentage by weight: 20% (wt) of organic acid sodium salt; 1.5% (wt) of sodium carbonate; 5.5% (wt) of hydroxide; and 73% (wt) of water.

[0035] Tartaric acid reacts with sodium carbonate and sodium hydroxide in the saponification waste alkali solution to increase the concentration of organic acid sodium salt in the grinding aid, thereby improving the grinding aid effect and playing a good grinding aid role.

[0036] The hydroxycarboxylate in the present invention can be selected from sodium gluconate, sodium citrate or sodium tartrate. In this embodiment, sodium gluconate is preferred, so that the oil in the sugar waste liquid can be removed by adsorption and chemical reaction, so that the sugar waste liquid has a better grinding aid effect.

[0037] The defoaming agent in the present invention can be selected from silicone defoaming agents and / or polyether-modified silicone additives. In this embodiment, polyether-modified silicone additives are preferred.

[0038] In the present invention, the cement accelerator can be selected from at least one of triisopropanolamine, triethanolamine, ethylene glycol, polyethylene glycol and calcium hydroxide. Wherein, polyethylene glycol is a low molecular weight polyethylene glycol. In this embodiment, a solution obtained by mixing triethanolamine and polyethylene glycol in a ratio of 1:1 is preferably used as the cement accelerator in the cement raw material additive.

[0039] The present invention provides a method for preparing a cement raw material additive, specifically comprising mixing and stirring 2.8 parts of hydroxycarboxylate, 3 parts of sugar waste liquid, 92 parts of saponification waste alkali liquid, 1.2 parts of tartaric acid, 0.5 parts of defoamer and 0.5 parts of cement accelerator by weight for 5 hours. After the reaction is completed, the cement raw material additive of the present embodiment is obtained.

[0040] Comparative Example 1

[0041] In this comparative example, except that hydroxycarboxylate and sugar waste liquid were not added, and the contents of other components were slightly adjusted, everything else was the same as Example 3.

[0042] Comparative Example 2

[0043] In this comparative example, except that hydroxycarboxylate is not added and the contents of other components are slightly adjusted, everything else is the same as Example 3.

[0044] Comparative Example 3

[0045] In this comparative example, except that no sugar waste liquid is added and the contents of other components are slightly adjusted, everything else is the same as Example 3.

[0046] In order to prove the influence of simultaneous addition of hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor on cement construction performance, the applicant added the cement raw material additives of Examples 1-3 and Comparative Examples 1-3 into cement raw material. The specific test method is shown in "National Standard of the People's Republic of China GB / T 1345 Cement Fineness Test Method Sieve Analysis Method", and the specific test conditions and results are shown in Table 1.

[0047] Table 1

[0048]

[0049]

[0050] From the results in Table 1, it can be seen that the simultaneous addition of hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor, compared with no addition of hydroxycarboxylate and sugar waste liquor (Comparative Example 1) or no addition of one of hydroxycarboxylate and sugar waste liquor (Comparative Example 2 and Comparative Example 3), the 80-micron sieve residue of the material decreased, indicating that the fineness was improved, indicating that the simultaneous addition of hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor makes the cement raw material additive have a good grinding aid effect.

[0051] The cement raw material additives of Examples 1-3 of the present invention and Comparative Examples 1-3 (added during the cement raw material grinding process) were used to test the compressive strength and flexural strength of cement clinker. The specific test method is shown in "National Standard of the People's Republic of China GB / T17671 Cement Mortar Strength Test Method (ISO Method)", and the specific test results are shown in Table 2.

[0052] Table 2

[0053]

[0054] From the results in Table 2, it can be seen that the simultaneous addition of hydroxycarboxylates, sugar waste liquor and saponification waste alkali liquor improves the flexural strength and compressive strength of the obtained cement raw material additive to a certain extent, indicating that the synergistic effect of hydroxycarboxylates, sugar waste liquor and saponification waste alkali liquor improves the compressive and flexural strengths of cement.

[0055] The above description is a detailed description of the preferred feasible embodiments of the present invention, but the embodiments are not intended to limit the scope of the patent application of the present invention. All equivalent changes or modified changes completed under the technical spirit suggested by the present invention should fall within the patent scope covered by the present invention.

Claims

1. A cement raw material additive, characterized in that: The cement raw material additive contains hydroxycarboxylate, sugar waste liquor and saponification waste alkali liquor, wherein the weight of the hydroxycarboxylate accounts for 0.1-5% of the weight of the cement raw material additive, the weight of the sugar waste liquor accounts for 0.5-5% of the weight of the cement raw material additive, and the weight of the saponification waste alkali liquor accounts for 90-98% of the weight of the cement raw material additive; the saponification waste alkali liquor contains water accounting for 45-75% of the weight of the saponification waste alkali liquor, organic acid sodium salt accounting for 5-25% of the weight of the saponification waste alkali liquor, and sodium hydroxide accounting for 5.5-6.5% of the weight of the saponification waste alkali liquor.

2. The cement raw material additive according to claim 1, characterized in that: The saponification waste alkali liquid is the saponification waste alkali liquid generated in the process of producing cyclohexanone by air oxidation of cyclohexane.

3. The cement raw material additive according to claim 1, characterized in that: The pH of the saponification waste alkali solution is ≥13, and the solid content is ≥32% (wt).

4. The cement raw material additive according to claim 1, characterized in that: The cement raw material additive also contains tartaric acid, and the weight of the tartaric acid accounts for 1-1.5% of the weight of the cement raw material additive.

5. The cement raw material additive according to claim 1, characterized in that: The hydroxycarboxylate is sodium gluconate, sodium citrate or sodium tartrate.

6. The cement raw material additive according to claim 1, characterized in that: The cement raw material additive further contains a defoamer, the weight of the defoamer accounts for 0.1-1% of the weight of the cement raw material additive, and the defoamer includes an organosilicon defoamer and / or a polyether modified silicon additive.

7. The cement raw material additive according to claim 1, characterized in that: The cement raw material additive also contains a cement accelerator, the weight of the cement accelerator accounts for 0.1-1% of the weight of the cement raw material additive, and the cement accelerator includes at least one of triisopropanolamine, triethanolamine, ethylene glycol, polyethylene glycol and calcium hydroxide.

8. The cement raw material additive according to claim 7, characterized in that: The polyethylene glycol is a low molecular weight polyethylene glycol.

9. A method for preparing a cement raw material additive, characterized in that: Specifically, 0.1-5 parts of hydroxycarboxylate, 0.5-5 parts of sugar waste liquid, 90-98 parts of saponification waste alkali liquid, 1-1.5 parts of tartaric acid, 0.1-1 parts of defoaming agent and 0.1-1 parts of cement accelerator are mixed and stirred for reaction for 4-5 hours.

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