A mineralizer for raw cement meal with photocatalytic excitation mineralization effect, its preparation method and application

Abstract

This application relates to the technical field of cement mineralizers, and specifically discloses a cement raw material mineralizer with a photocatalytic excitation mineralization effect, its preparation method and application. The cement raw material mineralizer with a photocatalytic excitation mineralization effect provided by this application specifically includes the following components in parts by weight: 9-14 parts of nitrate, 4-8 parts of CdSe quantum dots, 2-4 parts of multi-walled carbon nanotubes, 20-30 parts of fluorite waste residue, and 44-65 parts of fly ash; the nitrate is composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 8-12:1-2. The technical solution of this application can stimulate the mineralization components in the fluorite waste residue through the design of the quantum dot-photocatalytic hybrid, significantly improving the mineralization efficiency of the mineralizer and enhancing the comprehensive performance of the cement product.

Description

Technical Field

[0001] The present application relates to the technical field of cement mineralizers, and specifically relates to a cement raw meal mineralizer with a photocatalytic excitation mineralization effect, its preparation method and application. Background Art

[0002] At present, in the cement production process, the use of mineralizers is crucial for improving production efficiency and product performance. However, traditional mineralizers have problems such as insufficient efficiency, high energy consumption and heavy environmental burden, and there is an urgent need for innovative solutions.

[0003] At present, conventional mineralizers mostly use chemical substances. Although they can improve the mineralization efficiency to a certain extent, they are often accompanied by an increase in energy consumption and the risk of environmental pollution. Defects of the prior art: Traditional mineralizers cannot achieve high-efficiency mineralization while taking into account environmental friendliness and sustainability. In addition, the prior art lacks intelligent control means and is difficult to adjust flexibly according to the actual production situation. Summary of the Invention

[0004] In order to solve the above technical problems, the present application provides a cement raw meal mineralizer with a photocatalytic excitation mineralization effect, its preparation method and application.

[0005] The present application provides a cement raw meal mineralizer with a photocatalytic excitation mineralization effect, which specifically includes the following components in parts by weight: 9-14 parts of nitrate, 4-8 parts of CdSe quantum dots, 2-4 parts of multi-walled carbon nanotubes, 20-30 parts of fluorite waste residue, 44-65 parts of fly ash; the nitrate is composed of a mixture of ferric nitrate and cobalt nitrate with a weight ratio of 8-12:1-2.

[0006] The present application adopts the above technical solution to construct a CdSe quantum dot-embedded multi-level pore carbon nanotube network by using a quantum dot nanonetwork catalytic architecture, and uses electrophoresis deposition to ensure the precise positioning and high dispersion of quantum dots between carbon nanotubes, forming a three-dimensional interconnected structure, which greatly increases the specific surface area and active sites; the nitrate-doped layer is prepared by an in-situ growth method, which not only strengthens the thermal stability of the structure, but also promotes the high-efficiency catalysis of fluorite waste residue at high temperature and acts on the thermal decomposition reaction of calcium carbonate. In addition, the unique grid structure in the photocatalytic mineralizer promotes the superior contact between the material and the reaction medium, and optimizes the long-term stability and reaction compatibility of the material in silicate synthesis.

[0007] The present application uses micro-nano structure regulation and dispersion technology to optimize the pore structure and specific surface area of carbon nanotubes, ensure the uniform dispersion of the mineralizer in the cement raw meal, increase the number of active sites, promote the completion of the mineralization reaction, reduce energy consumption, and improve the performance indicators of cement. Through the design of a quantum dot-photocatalysis hybrid, the mineralization components in the fluorite waste residue are excited, significantly improving the mineralization efficiency and enhancing the comprehensive performance of the cement product.

[0008] Preferably, the cement raw material mineralizer with photocatalytically stimulated mineralization effect specifically comprises the following components in parts by weight: 10-13 parts of nitrate, 5-7 parts of CdSe quantum dots, 2.5-3.5 parts of multi-walled carbon nanotubes, 20-30 parts of fluorite waste residue, and 44-65 parts of fly ash.

[0009] Preferably, the cement raw material mineralizer with photocatalytically stimulated mineralization effect specifically comprises the following components in parts by weight: 10-13 parts of nitrate, 5-7 parts of CdSe quantum dots, 2.5-3.5 parts of multi-walled carbon nanotubes, 23-28 parts of fluorite waste slag, and 50-60 parts of fly ash.

[0010] Preferably, the cement raw material mineralizer with photocatalytically stimulated mineralization effect specifically comprises the following components in parts by weight: 11 parts of nitrate, 6 parts of CdSe quantum dots, 3 parts of multi-walled carbon nanotubes, 26 parts of fluorite waste residue, and 55 parts of fly ash.

[0011] Through experimental analysis, it can be known that the amount of each raw material component has a great influence on the performance of the photocatalytic mineralizer. The present application further improves the application performance of the photocatalytic mineralizer by controlling the amount of each raw material component to be within the above range.

[0012] Specifically, the CdSe quantum dots are Aladdin oil-soluble CdSe quantum dots, which are diluted 90-110 times with an organic solvent to obtain

[0013] Specifically, the size specifications of the multi-walled carbon nanotubes are: multi-walled carbon nanotubes (short)>50 nm, purity 95%, length 0.5-2 microns, and diameter 50 nm.

[0014] Specifically, the particle size of the fluorite waste is less than 100 mesh.

[0015] Preferably, the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 9-11:1.2-1.8.

[0016] Preferably, the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 10:1.5.

[0017] In a specific embodiment, in the nitrate, the weight ratio of iron nitrate to cobalt nitrate can be 8-9:1, 8-9:1.2, 8:1.2-1.5, 8:1.8-2, 8-10:2, 9-10:1, 9-11:1.2, 9-10:1.5, 9:1.2-1.8, 9:1.2-2, 10-11:1, 10-11:1.2, 10-11:1.5, 10-11:1.8, 10:1.5-2, 11-12:1, 11-12:1.2, 11:1.2-1.5, 11:1.2-1.8, 11:1.5-2, 12:1-1.5, 12:1.5-1.8, 12:1.8-2, 12:1-2.

[0018] In some specific embodiments, in the nitrate, the weight ratio of iron nitrate to cobalt nitrate can also be 8:1, 8:1.2, 8:1.5, 8:1.8, 8:2, 9:1, 9:1.2, 9:1.5, 9:1.8, 9:2, 10:1, 10:1.2, 10:1.5, 10:1.8, 10:2, 11:1, 11:1.2, 11:1.5, 11:1.8, 11:2, 12:1, 12:1.5, 12:1.8, 12:2.

[0019] Through experimental analysis, it can be known that by controlling the weight ratio of iron nitrate to cobalt nitrate in the nitrate within the above range, the application performance of the photocatalytic mineralizer is further improved.

[0020] In a second aspect, the present application provides a preparation method of the above cement raw meal mineralizer with photocatalytic excitation mineralization effect, specifically including the following steps in sequence:

[0021] Weigh the respective raw material components in corresponding weight portions, dissolve the iron nitrate and the cobalt nitrate in water, then add the CdSe quantum dots and the multi-walled carbon nanotubes, and form a modified CdSe quantum dot-carbon nanotube composite structure solution through electrophoretic deposition;

[0022] Add the fluorite waste residue and the fly ash to the above modified CdSe quantum dot-carbon nanotube composite structure solution for mixing, and dry it to obtain the cement raw meal mineralizer with photocatalytic excitation mineralization effect.

[0023] Preferably, the electrophoretic deposition voltage uses a 6-18V DC voltage, and the pH of the electrophoresis solution is 2-4.

[0024] In a third aspect, the present application provides a cement raw meal, which is prepared by using the above cement raw meal mineralizer with photocatalytic excitation mineralization effect.

[0025] In a fourth aspect, the present application provides a method for preparing the above-mentioned cement raw meal, which specifically comprises the following steps in sequence: adding the high-efficiency photocatalytic mineralizer into the raw meal at a ratio of 0.1-0.3% at the raw meal feeding belt, and grinding it together with the raw meal.

[0026] In summary, the technical solution of this application has the following effects:

[0027] The technology of this application mainly relates to the field of cement raw material mineralizer, its preparation method and application and intelligent application technology; the cement raw material mineralizer with photocatalytic excitation mineralization effect prepared by this application is suitable for the cement production process, improving mineralization efficiency, improving cement performance indicators, and ensuring that the production process meets the application scenarios of green and low-carbon standards.

[0028] This application uses micro-nanostructure regulation and dispersion technology to optimize the pore structure and specific surface area of ​​carbon nanotubes, ensure the uniform dispersion of mineralizers in cement raw materials, increase the number of active sites, promote the completeness of mineralization reactions, reduce energy consumption, and improve cement performance indicators. Through the design of quantum dot-photocatalytic hybrids, the mineralized components in fluorite waste residue are stimulated, the mineralization efficiency is significantly improved, and the comprehensive performance of cement products is enhanced. Compared with the existing technology, this technology mainly solves the technical problems of low efficiency, high energy consumption, heavy environmental burden, and lack of intelligent control methods in the process of cement raw material mineralization. DETAILED DESCRIPTION

[0029] The present application is further described in detail below in conjunction with examples, comparative examples and performance testing experiments. These examples should not be construed as limiting the scope of protection claimed in the present application.

[0030] CdSe quantum dots: Aladdin oil-soluble CdSe quantum dots, diluted 100 times with alcohol, take 1g CdSe quantum dots, 99g alcohol, mix them to get the CdSe quantum dots for use; Multi-walled carbon nanotubes (Xianfeng Nano): multi-walled carbon nanotubes (short) >50 nm, purity 95%, length 0.5-2 microns, diameter 50nm; fluorite waste residue: 100 mesh; fly ash: fly ash from power plant.

[0031] Example

[0032] Examples 1-9

[0033] Examples 1-9 respectively provide a cement raw material mineralizer having a photocatalytically stimulated mineralization effect and a preparation method thereof.

[0034] The difference between the above embodiments is that the dosage of each component in the cement raw material mineralizer with photocatalytic excitation mineralization effect is different, as shown in Table 1.

[0035] The preparation method of the cement raw material mineralizer with photocatalytic excitation mineralization effect in the above embodiments is as follows:

[0036] Weigh the respective raw material components in corresponding weight portions. Dissolve the nitrate (composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 10:1.5) in water, add CdSe quantum dots and multi-walled carbon nanotubes, and form a modified CdSe quantum dot-carbon nanotube composite structure solution by electrophoretic deposition. The electrophoretic deposition voltage is a 12V DC voltage, and the pH of the electrophoresis solution is 3.

[0037] Add fluorite waste residue and fly ash into the above-mentioned modified CdSe quantum dot-carbon nanotube composite structure solution, mix evenly, and dry to obtain a cement raw material mineralizer with photocatalytic excitation mineralization effect.

[0038] Table 1 Dosages of each component in the cement raw material mineralizer with photocatalytic excitation mineralization effect in Examples 1-9

[0039]

[0040] Examples 10-13

[0041] Examples 10-13 respectively provide a cement raw material mineralizer with photocatalytic excitation mineralization effect and its preparation method.

[0042] The differences between the above embodiments and Example 2 are specifically as follows: The composition of the nitrate is different, as shown below.

[0043] In Example 10: The nitrate is composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 8:2 (i.e., 4:1).

[0044] In Example 11: The nitrate is composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 12:1.

[0045] In Example 12: The nitrate is composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 9:1.8.

[0046] In Example 13: The nitrate is composed of a mixture of iron nitrate and cobalt nitrate with a weight ratio of 11:1.2.

[0047] For the above embodiments, the types of the remaining raw material components, the dosages of each raw material, and the process parameters of the preparation method are the same as those in Example 2.

[0048] Examples 14-17

[0049] Examples 14-17 respectively provide a cement raw material mineralizer with photocatalytic excitation mineralization effect and its preparation method.

[0050] The differences between the above embodiments and Example 2 are specifically as follows: The process parameters of electrophoretic deposition are different, as shown below.

[0051] In Example 14: The electrophoretic deposition voltage is a 6V DC voltage, and the pH of the electrophoretic solution is 4.

[0052] In Example 15: The electrophoretic deposition voltage is an 18V DC voltage, and the pH of the electrophoretic solution is 2.

[0053] In Example 16: The electrophoretic deposition voltage is a 9V DC voltage, and the pH of the electrophoretic solution is 3.5.

[0054] In Example 17: The electrophoretic deposition voltage is a 15V DC voltage, and the pH of the electrophoretic solution is 2.5.

[0055] In the above examples, the types of raw material components, the dosages of each raw material, and other process parameters of the preparation method are the same as those in Example 2. Comparative Example

[0056] Comparative Examples 1-5

[0057] Comparative Examples 1-5 respectively provide a photocatalytic mineralizer and a preparation method thereof.

[0058] The differences between the above comparative examples and Example 2 are as follows: The dosages of each component in the cement raw meal mineralizer with photocatalytic excitation mineralization effect are different, as specifically shown in Table 2.

[0059] Table 2 Dosages of each component in the cement raw meal mineralizer with photocatalytic excitation mineralization effect in Comparative Examples 1-5

[0060]

[0061] In the above comparative examples, other process parameters are the same as those in Example 2.

[0062] Comparative Examples 6-7

[0063] Comparative Examples 6-7 respectively provide a cement raw meal mineralizer with catalytic effect and a preparation method thereof.

[0064] The differences between the above comparative examples and Example 2 are specifically as follows.

[0065] In Comparative Example 6: The nitrate is composed of a mixture of iron nitrate and potassium nitrate with a weight ratio of 10:1.5.

[0066] In Comparative Example 7: The nitrate is composed of a mixture of cobalt nitrate and iron nitrate with a weight ratio of 10:1.5.

[0067] In the above comparative examples, the types of the remaining raw material components, the dosages of each raw material, and other process parameters of the preparation method are the same as those in Example 2. Comparative Example 8

[0068] Comparative Example 8 provides a mineralizer.

[0069] In this comparative example, the mineralizer is fluorite waste residue.

[0070] Performance detection test

[0071] The high-efficiency photocatalytic mineralizer prepared by the examples and comparative examples was tested in a dry-process cement production line. The raw material mill adopted the grinding process of a roller press + a separator. The addition amount of the mineralizer was 0.1% of the total mass of the raw materials. The standard coal consumption per ton of clinker, the strength of the clinker at 3d, 7d, and 28d, and the sulfur content in the flue gas (mg / m 3 ) were detected.

[0072] Detection results: As shown in Table 3.

[0073] Table 3 Performance detection results of the mineralizers in Examples 1-17 and Comparative Examples 1-8

[0074]

[0075] By analyzing Table 3 and comparing the performance detection results of the photocatalytic mineralizers in the examples and comparative examples, it can be concluded that the quantum dot component in the cement raw material mineralizer with photocatalytic excitation mineralization effect prepared by the technical solution provided by this application can act on the fluorite waste residue and stimulate the mineralization components in the fluorite waste residue, improving the mineralization effect of the fluorite waste residue.

[0076] By comparing the performance detection results of the photocatalytic mineralizers in Examples 1-9 and Comparative Examples 4-5, it can be seen that the dosage of each raw material component has a great influence on the performance of the photocatalytic mineralizer. By controlling the dosage of each raw material component in this application, the application performance of the photocatalytic mineralizer is further improved.

[0077] By comparing the performance detection results of the photocatalytic mineralizers in Example 2 and Examples 10-13, it can be seen that by controlling the weight ratio of iron nitrate and cobalt nitrate in the nitrate to be 9-11:1.2-1.8 in this application, the application performance of the photocatalytic mineralizer is further improved.

[0078] Although the present invention has been described in detail above with general descriptions and specific embodiments, based on the present invention, some modifications or improvements can be made, which are obvious to those skilled in the art. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection required by the present invention.

Claims

1. A cement raw material mineralizer with photocatalytic excitation mineralization effect, characterized in that Specifically, it includes the following components in parts by weight: 9-14 parts of nitrate, 4-8 parts of CdSe quantum dots, 2-4 parts of multi-walled carbon nanotubes, 20-30 parts of fluorite waste residue, and 44-65 parts of fly ash; The nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 8-12:1-2; The method for preparing the cement raw material mineralizer having a photocatalytically stimulated mineralization effect specifically comprises the following steps in sequence: Weighing the corresponding weight portions of the raw material components respectively, dissolving the ferric nitrate and the cobalt nitrate in water, and then adding the CdSe quantum dots and the multi-walled carbon nanotubes to form a modified CdSe quantum dot-carbon nanotube composite structure solution by electrophoretic deposition; The fluorite waste residue and the fly ash are added to the modified CdSe quantum dot-carbon nanotube composite structure solution, mixed evenly, and dried to obtain the cement raw material mineralizer with photocatalytic excitation mineralization effect.

2. The mineralizer for cement raw meal with photocatalytic excitation mineralization effect according to claim 1, characterized in that, Specifically, the invention comprises the following components in parts by weight: 10-13 parts of nitrate, 5-7 parts of CdSe quantum dots, 2.5-3.5 parts of multi-walled carbon nanotubes, 23-28 parts of fluorite waste residue, and 50-60 parts of fly ash.

3. The mineralizer for cement raw meal with photocatalytic excitation mineralization effect according to claim 1, characterized in that, Specifically, the invention comprises the following components in parts by weight: 11 parts of nitrate, 6 parts of CdSe quantum dots, 3 parts of multi-walled carbon nanotubes, 26 parts of fluorite waste residue, and 55 parts of fly ash.

4. The mineralizer for cement raw meal with photocatalytic excitation mineralization effect according to claim 1, characterized in that, The CdSe quantum dots are Aladdin oil-soluble CdSe quantum dots, which are obtained by diluting an organic solvent by 90-110 times.

5. The mineralizer for cement raw meal with photocatalytic excitation mineralization effect according to claim 1, characterized in that The nitrate is composed of a weight ratio of 9-11: It is composed of a mixture of 1.2-1.8 iron nitrate and cobalt nitrate.

6. The mineralizer for cement raw meal with photocatalytic excitation mineralization effect according to claim 1, characterized in that, The nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 10:1.

5.

7. The preparation method of the cement raw material mineralizer with photocatalytic excitation mineralization effect according to any one of claims 1-6, characterized in that, Specifically, the following steps are performed in sequence: Weighing the corresponding weight portions of the raw material components respectively, dissolving the ferric nitrate and the cobalt nitrate in water, and then adding the CdSe quantum dots and the multi-walled carbon nanotubes to form a modified CdSe quantum dot-carbon nanotube composite structure solution by electrophoretic deposition; The fluorite waste residue and the fly ash are added to the modified CdSe quantum dot-carbon nanotube composite structure solution, mixed evenly, and dried to obtain the cement raw material mineralizer with photocatalytic excitation mineralization effect.

8. The preparation method of the cement raw material mineralizer with photocatalytic excitation mineralization effect according to claim 7, characterized in that, The electrophoretic deposition voltage is 6-18V DC voltage, and the pH of the electrophoretic solution is 2-4.

9. A cement raw meal, characterized in that, The cement raw material mineralizer having a photocatalytically stimulated mineralization effect is prepared using any one of claims 1 to 6.

10. The preparation method of the cement raw meal according to claim 9, characterized in that, Specifically, the following steps are sequentially performed: adding the cement raw material mineralizer with photocatalytic excitation mineralization effect into the raw material at a ratio of 0.1-0.3% at the raw material feeding belt, and grinding together with the raw material.

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