Cement mineralizer as well as preparation method and application thereof

Abstract

The invention relates to the technical field of cement production, and particularly discloses a cement mineralizer as well as a preparation method and application thereof. The cement mineralizing agent is prepared from the following raw material components in parts by weight: 15 to 25 parts of N-methyldiethanolamine, 8 to 20 parts of polytetramethylene ether glycol, 2 to 8 parts of citric acid, 6 to 12 parts of modified aluminum hydroxide and 1 to 3 parts of glycine, wherein the modified aluminum hydroxide is aluminum hydroxide modified by bis (dioctyloxy pyrophosphate) ethanediolato titanate and sodium lauroyl methyl aminopropionate. The cement mineralizer disclosed by the invention does not contain sulfur and chromium, is small in environmental pollution, has relatively excellent alkaline absorption capacity and stability, and can improve the fluidity and durability of cement and promote the hydration reaction of the cement, so that the early strength of concrete is improved.

Description

Technical Field

[0001] The present application relates to the technical field of cement production, and in particular to a cement mineralizer and a preparation method and application thereof. Background Art

[0002] Cement mineralizer, also known as cement grinding enhancer, cement mineralizer, etc., is a chemical additive that can improve the grinding effect and performance of cement and increase the strength of cement. On the basis of using cement grinding aids, it can further improve the strength and hourly output of cement and improve the adaptability of cement.

[0003] At present, sulfur or chromium is added to most cement mineralizers. The sulfur ions in sulfur-type mineralizers can react with metal ions to form sulfides, which can further react with other ions in the solution to form more stable mineral phases, thereby accelerating the mineralization process; while chromium ions can act as inhibitors or promoters of crystal growth, controlling the particle size and morphology of minerals by affecting the nucleation and growth process of mineral crystals.

[0004] However, sulfur-based mineralizers will generate volatile SO during the calcination of clinker. 2 、SO 3 Corrosive gases not only corrode cement equipment, but also seriously pollute the environment through sulfur waste gas discharged into the air. Chromium ions will leach out during the use of cement materials as water penetrates and dries, which will have adverse effects on water sources, the environment, and the health of personnel. Therefore, it is necessary to develop a cement mineralizer that does not contain sulfur and chromium to reduce the pollution caused by cement production to the environment. Summary of the invention

[0005] In order to solve the problem that sulfur or chromium elements in cement mineralizers may cause environmental pollution, the present application provides a cement mineralizer and a preparation method and application thereof. The cement mineralizer in the present application does not contain sulfur and chromium, has low environmental pollution, and has excellent alkaline absorption capacity and stability, can improve the fluidity and durability of cement, promote the hydration reaction of cement, and thus improve the early strength of concrete.

[0006] In the first aspect, the present application provides a cement mineralizer, which adopts the following technical solution: A cement mineralizer, wherein the raw materials for preparing the cement mineralizer include the following components in parts by weight: 15-25 parts of N-methyldiethanolamine, 8-20 parts of polytetramethylene ether glycol, 2-8 parts of citric acid, 6-12 parts of modified aluminum hydroxide and 1-3 parts of glycine; wherein the modified aluminum hydroxide is aluminum hydroxide modified by bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylaminopropionate.

[0007] By adopting the above technical scheme, N-methyldiethanolamine can react chemically with calcium ions in cement, accelerate the hydration and hardening process of cement, improve the early strength of concrete, and also play a water-reducing role, reduce the amount of water in concrete, improve the density and durability of concrete, and improve the calcinability of cement. Polytetramethylene ether glycol can improve the fluidity of cement paste, reduce water seepage, improve the dispersibility of cement, and make cement more evenly mixed with water, thereby improving the strength and density of concrete. In addition, it can also play a lubricating role and improve the construction performance of cement. Citric acid is an organic acid that can adjust the pH value of cement paste so that it is within a suitable range, which is conducive to the hydration and hardening of cement. It can also react with gypsum and other components in cement to form calcium sulfonate, accelerate the hydration rate of cement, and improve the early strength of concrete. Modified aluminum hydroxide, as an alkaline absorbent, can also adjust the pH value of cement paste, promote the hydration reaction of cement, thereby improving the strength of cement. Modified aluminum hydroxide also has a certain gelling property, which can improve the performance and durability of concrete. Glycine is also an organic acid. While adjusting the pH value of cement paste, the amino and carboxyl groups in it will react with the metal ions in cement to promote the hydration reaction of cement, thereby accelerating cement hardening.

[0008] In addition, citric acid and part of modified aluminum hydroxide can react to form aluminum citrate, which has alkaline absorption capacity, while glycine can form stable chelates with metal ions to promote the dispersion and stability of aluminum hydroxide. The compound of citric acid, modified aluminum hydroxide and glycine can promote each other and improve the alkaline absorption effect and stability of cement mineralizer.

[0009] Preferably, the raw materials for preparing the cement mineralizer include the following components in parts by weight: 18-22 parts of N-methyldiethanolamine, 12-16 parts of polytetramethylene ether glycol, 3-6 parts of citric acid, 7-10 parts of modified aluminum hydroxide and 1-3 parts of glycine.

[0010] By adopting the above technical solution, the dosage of raw materials for preparing cement mineralizers is further optimized, which helps to improve the stability of cement mineralizers and improve the strengthening effect of cement mineralizers on cement properties.

[0011] Preferably, the mass ratio of citric acid, modified aluminum hydroxide and glycine is (1-4):(3-6):1.

[0012] By adopting the above technical solution and further adjusting the mass ratio of citric acid, modified aluminum hydroxide and glycine, it is helpful to improve the alkaline absorption capacity and stability of the cement mineralizer, thereby promoting the hydration reaction of cement and improving the early strength of concrete.

[0013] In some preferred embodiments, the mass ratio of citric acid, modified aluminum hydroxide and glycine can be 3:4:1, 1:6:1 or 4:3:1, etc.

[0014] Preferably, the modified aluminum hydroxide is obtained by the following steps: S1, bis(dioctyloxypyrophosphate)ethylene titanate, sodium lauroylmethylaminopropionate and isopropyl alcohol are uniformly mixed to obtain a modified mixed solution; S2. Add the aluminum hydroxide to the modified mixed solution, stir for 8-15 hours, then wash, dry and crush to obtain the modified aluminum hydroxide.

[0015] By adopting the above technical scheme, bis(dioctyloxypyrophosphate)ethylene titanate will react with the hydroxyl groups on the surface of aluminum hydroxide to form chemical bonds, thereby enhancing the interfacial properties and compatibility of aluminum hydroxide and improving the dispersibility and stability of aluminum hydroxide; while sodium lauroylmethylaminopropionate can reduce the surface tension of aluminum hydroxide, prevent powder particle agglomeration, and improve the fluidity and dispersibility of the powder. The combined use of the two can further improve the dispersibility of the modified aluminum hydroxide and its compatibility with other preparation raw materials, thereby improving its alkaline absorption capacity.

[0016] Preferably, the mass ratio of the bis(dioctyloxypyrophosphate)ethylene titanate to sodium lauroylmethylaminopropionate is 1:(1-3).

[0017] By adopting the above technical scheme, further adjusting the mass ratio of bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylaminopropionate can help optimize the modification effect of aluminum hydroxide, thereby further improving the alkaline absorption capacity of the modified aluminum hydroxide.

[0018] In some preferred embodiments, the mass ratio of the bis(dioctyloxypyrophosphate)ethylene titanate to sodium lauroylmethylaminopropionate can be 1:1, 1:2 or 1:3, etc.

[0019] Preferably, the mass volume ratio of the aluminum hydroxide to the modified mixed liquid is 1:(10-20).

[0020] By adopting the above technical solution, the mass volume ratio of aluminum hydroxide and the modified mixed liquid is further adjusted, so as to reduce the modification cost as much as possible while ensuring the modification effect of aluminum hydroxide.

[0021] In some preferred embodiments, the mass volume ratio of the aluminum hydroxide to the modified mixed solution can be 1:10, 1:15 or 1:20, etc.

[0022] Preferably, the raw materials for preparing the cement mineralizer also include 1-4 parts of stabilizer.

[0023] By adopting the above technical solution, the stabilizer can inhibit or slow down the chemical and physical changes of cement mineralizer during storage and use, prevent its decomposition, precipitation, crystallization or agglomeration, and thus maintain its original performance and activity. At the same time, the stabilizer can also adjust the pH value of cement mineralizer, inhibit the generation of harmful substances, and improve the durability and impermeability of concrete.

[0024] Preferably, the stabilizer is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate, urea, ethylene glycol and glycerol.

[0025] By adopting the above technical solution, the phosphate groups, amide groups or hydroxyl groups in the molecular structure of the above stabilizer will chemically react with the calcium ions in the cement to generate stable complexes. These complexes can play a role of dispersion and stabilization in the cement paste, preventing the aggregation and precipitation of cement particles, thereby improving the fluidity and strength of the cement; in addition, the above stabilizer can delay the hydration and hardening process of cement, so that the concrete has better construction performance.

[0026] In a second aspect, the present application provides a method for preparing a cement mineralizer, using the following technical solution: A method for preparing a cement mineralizer comprises the following steps: uniformly mixing N-methyldiethanolamine, polytetramethylene ether glycol, citric acid, modified aluminum hydroxide and other preparation raw materials to prepare the cement mineralizer.

[0027] By adopting the above technical scheme, the preparation method adopted in the present application is relatively simple, does not require too much equipment, is easy to produce, and is simple and efficient.

[0028] In a third aspect, the present application provides a use of the cement mineralizer as described above or the cement mineralizer prepared by the above preparation method in cement clinker firing.

[0029] After the cement mineralizer of the present application is added during the raw material calcination process, on the one hand, it can react with calcium ions in cement to generate stable complexes, thereby increasing the fluidity of cement paste, improving its construction performance, accelerating the hydration and hardening process of cement, and increasing the early strength of concrete; on the other hand, the cement mineralizer of the present application does not contain sulfur and chromium elements, which significantly reduces pollution to the environment and has broad application prospects.

[0030] In summary, the present application includes at least one of the following beneficial technical effects: 1. The combination of citric acid, modified aluminum hydroxide and glycine in the cement mineralizer of the present application can produce a synergistic effect, improve the alkaline absorption capacity of the cement mineralizer, enhance its stability, adjust the pH value of the cement paste, improve its fluidity and construction performance, thereby promoting the hydration reaction of cement and improving its early strength; 2. In this application, bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylaminopropionate are used to modify aluminum hydroxide, wherein bis(dioctyloxypyrophosphate)ethylene titanate reacts with the hydroxyl groups on the surface of aluminum hydroxide to form chemical bonds, thereby enhancing the interfacial properties and compatibility of aluminum hydroxide and improving the dispersibility and stability of aluminum hydroxide; while sodium lauroylmethylaminopropionate can reduce the surface tension of aluminum hydroxide, prevent powder particle agglomeration, and improve the fluidity and dispersibility of the powder. The combination of the two can enhance the alkaline absorption capacity of the modified aluminum hydroxide and further enhance the early strength of cement. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is a flow chart for the preparation of modified aluminum hydroxide in the cement mineralizer of this application. DETAILED DESCRIPTION

[0032] In order to make the present application easier to understand, the present application will be further described in detail below in conjunction with the examples, which are merely illustrative and are not intended to limit the scope of application of the present application. The raw materials or components used in the present application can be obtained through commercial routes or conventional methods unless otherwise specified.

[0033] Source of raw materials Polytetramethylene ether glycol, molecular weight is 305.43, density (25℃) is 1g / mL, melting point is 33-36℃, content is 98%; bis(dioctyloxypyrophosphate)ethylene titanate, effective substance content is 98%, grade is superior; sodium tripolyphosphate, effective ingredient content is 96%, grade is superior.

[0034] Preparation Example 1: Reference Figure 1 The preparation method of modified aluminum hydroxide is as follows: S1, 6 kg of bis(dioctyloxypyrophosphate)ethylene titanate, 6 kg of sodium lauroylmethylaminopropionate and 8 L of isopropanol are mixed evenly to obtain a modified mixed solution; S3, 1 kg of aluminum hydroxide is added to 10 L of the modified mixed solution, stirred for 12 hours, washed with isopropanol, dried at 45°C, and crushed to obtain modified aluminum hydroxide. Among them, the mass ratio of bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylaminopropionate is 1:1, and the mass volume ratio of aluminum hydroxide and the modified mixed solution is 1:10.

[0035] Preparation Example 2: The difference between Preparation Example 2 and Preparation Example 1 is that in the modified mixed solution, the amount of bis(dioctyloxypyrophosphate)ethylene titanate is 4 kg, the amount of sodium lauroylmethylaminopropionate is 8 kg, the mass ratio of bis(dioctyloxypyrophosphate)ethylene titanate to sodium lauroylmethylaminopropionate is 1:2, and the rest is the same as Preparation Example 1.

[0036] Preparation Example 3: The difference between Preparation Example 3 and Preparation Example 1 is that in the modified mixed solution, the amount of bis(dioctyl pyrophosphate)ethylene titanate is 3 kg, the amount of sodium lauroyl methylamino propionate is 9 kg, the mass ratio of bis(dioctyl pyrophosphate)ethylene titanate to sodium lauroyl methylamino propionate is 1:3, and the rest is the same as Preparation Example 1.

[0037] Preparation Example 4-5: The difference between Preparation Examples 4-5 and Preparation Example 2 is that in step S3, the amount of the modified mixed solution used is 15L and 20L respectively, the mass volume ratio of aluminum hydroxide to the modified mixed solution is 1:15 and 1:20 respectively, and the rest is the same as Preparation Example 2.

[0038] Comparative Preparation Example 1: The difference between Comparative Preparation Example 1 and Preparation Example 1 is that in the modified mixed solution, the amount of bis(dioctyloxypyrophosphate)ethylene titanate is 12 kg, the amount of sodium lauroylmethylaminopropionate is 0, and the rest is the same as Preparation Example 1.

[0039] Comparative Preparation Example 2: The difference between Preparation Example 2 and Preparation Example 1 is that in the modified mixed solution, the amount of bis(dioctyloxypyrophosphate)ethylene titanate is 0, the amount of sodium lauroylmethylaminopropionate is 12 kg, and the rest is the same as Preparation Example 1.

[0040] Embodiment 1-3: The raw materials for preparing the cement mineralizer in Examples 1-3 are shown in Table 1, wherein the modified aluminum hydroxide is selected from the modified aluminum hydroxide prepared in Preparation Example 1. The preparation method of the cement mineralizer in Examples 1-3 is as follows: N-methyldiethanolamine, polytetramethylene ether glycol, citric acid, modified aluminum hydroxide and glycine are uniformly mixed to prepare the cement mineralizer.

[0041] Table 1. Raw materials and dosage of cement mineralizers in Examples 1-8 (kg) Embodiment 4-5: The raw materials and dosage of the cement mineralizer in Example 4-5 are shown in Table 1. The difference between them and Example 1 is that the mass ratios of citric acid, modified aluminum hydroxide and glycine are 1:6:1 and 4:3:1, respectively, while the mass ratio of citric acid, modified aluminum hydroxide and glycine in Example 1 is 3:4:1, and the rest is the same as Example 1.

[0042] Embodiment 6-8: The difference between Examples 6-8 and Example 1 is that the raw materials for preparing the cement mineralizer also include sodium tripolyphosphate, and the dosage of sodium tripolyphosphate is shown in Table 1. The rest is the same as Example 1.

[0043] Embodiment 9-12: The difference between Examples 9-12 and Example 7 is that the modified aluminum hydroxide is selected from the modified aluminum hydroxide prepared in Preparation Examples 2-5, respectively, and the rest is the same as Example 7.

[0044] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is that in the raw materials for preparing the cement mineralizer, the amount of citric acid added is 0, the amount of modified aluminum hydroxide added is 12 kg, the amount of glycine added is 4 kg, and the rest is the same as Example 1.

[0045] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is that in the raw materials for preparing the cement mineralizer, the amount of citric acid added is 12 kg, the amount of modified aluminum hydroxide added is 0, the amount of glycine added is 4 kg, and the rest is the same as Example 1.

[0046] Comparative Example 3: The difference between Comparative Example 3 and Example 1 is that in the raw materials for preparing the cement mineralizer, the amount of citric acid added is 7 kg, the amount of modified aluminum hydroxide added is 9 kg, the amount of glycine added is 0, and the rest is the same as Example 1.

[0047] Comparative Example 4: The difference between Comparative Example 4 and Example 7 is that an equal amount of aluminum hydroxide is used in the raw material for preparing the cement mineralizer instead of modified aluminum hydroxide, and the rest is the same as Example 7.

[0048] Comparative Examples 5-6: The difference between Comparative Examples 5-6 and Example 7 is that the modified aluminum hydroxide is selected from the modified aluminum hydroxide prepared in Comparative Preparation Examples 1-2, and the rest is the same as Example 7.

[0049] Test Case The cement mineralizers of Examples 1-12 and Comparative Examples 1-6 were added to the cement raw material at 3% of the weight of the cement raw material. The cement raw material was ground by a vertical mill and calcined in a 5000t / d cement dry kiln to obtain the corresponding clinker. The raw materials for preparing the raw material were as follows: 3.7% iron powder, 3.3% clay and 93% limestone (CaO 57.21wt%, SiO 2 10.24wt%Al 2 O 3 0.98wt%, MgO 0.18wt%, Fe 2 O 3 0.34wt%, loss on ignition 31.05wt%).

[0050] The clinker prepared above was tested for performance, including the hourly output, setting time and compressive strength, wherein the setting time was tested with reference to GB / T1346-2011 "Test Method for Water Consumption, Setting Time and Stability of Cement Standard Consistency", and the compressive strength was tested with reference to GB / T17671-1999 "Test Method for Cement Mortar Strength (ISO Method)". The test results are shown in Table 2.

[0051] Table 2 It can be seen from the test results in Table 2 that the clinker obtained by calcining the raw materials to which the cement mineralizers of Examples 1-12 and Comparative Examples 1-6 were added has an initial setting time of 129-202 min, a final setting time of 182-301 min, a 3d compressive strength of 14.8-22.3 MPa, and a 28d compressive strength of 35.9-48.9 MPa.

[0052] It can be seen from the test data of Examples 1-5 and Comparative Examples 1-3 that the cement mineralizer prepared according to Example 1 has a greater improvement in the yield and performance of cement clinker. When the mass ratio of citric acid, modified aluminum hydroxide and glycine is 3:4:1, the synergistic effect between the three is better, and the pH value of the clinker can be adjusted, the production of harmful substances can be inhibited, and the durability and strength of the clinker can be improved.

[0053] It can be seen from the test data of Examples 6-8 that after sodium tripolyphosphate is added to the cement mineralizer, the phosphate groups in its molecular structure react with the calcium ions in the raw material to produce a stable complex, prevent the raw materials from agglomerating and precipitating, improve the fluidity of the slurry, and thus enhance the strength of the clinker.

[0054] From the test data of Examples 7, 9-10 and Comparative Examples 4-6, it can be seen that after aluminum hydroxide is modified by bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylamino propionate, the synergistic effect between the two can improve the compatibility of aluminum hydroxide with other raw materials and enhance the alkaline absorption capacity of cement mineralizers. In particular, when the mass ratio of bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylamino propionate is 1:2, the synergistic effect between the two is better, and the modification effect on aluminum hydroxide is better, thereby improving the performance of clinker.

[0055] It can be seen from the test data of Examples 7 and 11-12 that in the preparation process of modified aluminum hydroxide, when the mass volume ratio of aluminum hydroxide and the modified mixed liquid is 1:15, the alkaline absorption capacity of the modified aluminum hydroxide is stronger, which can accelerate the formation of clinker minerals and improve the strength and stability of the clinker.

[0056] It should be noted that the embodiments described above are only used to explain the present application and do not constitute any limitation to the present application. The present application is described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory words, rather than restrictive words. The present application may be modified as specified within the scope of the claims of the present application, and the present invention may be revised without departing from the scope and spirit of the present application. Although the present application described therein relates to specific methods, materials and embodiments, it does not mean that the present application is limited to the specific examples disclosed therein. On the contrary, the present application can be extended to all other methods and applications with the same functions.

Claims

1. A cement mineralizer, characterized in that: The raw materials for preparing the cement mineralizer include the following components by weight: 15-25 parts of N-methyldiethanolamine, 8-20 parts of polytetramethylene ether glycol, 2-8 parts of citric acid, 6-12 parts of modified aluminum hydroxide and 1-3 parts of glycine; Wherein, the modified aluminum hydroxide is aluminum hydroxide modified by bis(dioctyloxypyrophosphate)ethylene titanate and sodium lauroylmethylaminopropionate.

2. The cement mineralizer according to claim 1, characterized in that: The raw materials for preparing the cement mineralizer include the following components by weight: 18-22 parts of N-methyldiethanolamine, 12-16 parts of polytetramethylene ether glycol, 3-6 parts of citric acid, 7-10 parts of modified aluminum hydroxide and 1-3 parts of glycine.

3. The cement mineralizer according to claim 1, characterized in that: The mass ratio of the citric acid, modified aluminum hydroxide and glycine is (1-4):(3-6):

1.

4. The cement mineralizer according to any one of claims 1 to 3, characterized in that: The modified aluminum hydroxide is obtained by the following steps: S1, mixing bis(dioctyloxypyrophosphate)ethylene titanate, sodium lauroylmethylaminopropionate and isopropyl alcohol uniformly to prepare a modified mixed solution; S2. Add the aluminum hydroxide to the modified mixed solution, stir for 8-15 hours, then wash, dry and crush to obtain the modified aluminum hydroxide.

5. The cement mineralizer according to claim 4, characterized in that: The mass ratio of the bis(dioctyloxypyrophosphate)ethylene titanate to sodium lauroylmethylaminopropionate is 1:(1-3).

6. The cement mineralizer according to claim 4, characterized in that: The mass volume ratio of the aluminum hydroxide and the modified mixed liquid is 1:(10-20).

7. The cement mineralizer according to any one of claims 1 to 3, characterized in that: The raw materials for preparing the cement mineralizer also include 1-4 parts of stabilizer.

8. The cement mineralizer according to claim 7, characterized in that: The stabilizer is selected from one or more of sodium tripolyphosphate, sodium hexametaphosphate, urea, ethylene glycol and glycerol.

9. A method for preparing a cement mineralizer according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: uniformly mixing the N-methyldiethanolamine, polytetramethylene ether glycol, citric acid, modified aluminum hydroxide and other preparation raw materials to prepare the cement mineralizer.

10. Use of the cement mineralizer according to any one of claims 1 to 8 or the cement mineralizer prepared by the preparation method according to claim 9 in cement clinker firing.

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