Cement raw material mineralizer with photocatalytic excitation mineralization effect and preparation method and application thereof

Abstract

The invention relates to the technical field of cement mineralizing agents, and particularly discloses a cement raw material mineralizing agent with a photocatalytic excitation mineralizing effect as well as a preparation method and application of the cement raw material mineralizing agent. The cement raw material mineralizer with the photocatalytic excitation mineralization effect is specifically prepared from the following components in parts by weight: 9 to 14 parts of nitrate, 4 to 8 parts of CdSe quantum dots, 2 to 4 parts of multiwalled carbon nanotubes, 20 to 30 parts of fluorite waste residues and 44 to 65 parts of fly ash, the nitrate is formed by mixing ferric nitrate and cobalt nitrate according to the weight ratio of (8-12): (1-2). According to the technical scheme, through the design of the quantum dot-photocatalytic hybrid, mineralization components in the fluorite waste residues can be excited, the mineralization efficiency of the mineralizer is remarkably improved, and the comprehensive performance of a cement product is enhanced.

Description

Technical Field

[0001] The present application relates to the technical field of cement mineralizers, and in particular to a cement raw material mineralizer having a photocatalytically stimulated mineralization effect, and a preparation method and application thereof. Background Art

[0002] At present, the use of mineralizers in cement production is crucial to improving production efficiency and product performance. However, traditional mineralizers have problems such as insufficient efficiency, high energy consumption and heavy environmental burden, and innovative solutions are urgently needed.

[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 increased energy consumption and the risk of environmental pollution. The defects of the existing technology: traditional mineralizers cannot achieve efficient mineralization while taking into account environmental friendliness and sustainability. In addition, the existing technology lacks intelligent control means and is difficult to flexibly adjust 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 material mineralizer with photocatalytic excitation mineralization effect, and a preparation method and application thereof.

[0005] The present application provides a cement raw material mineralizer with a photocatalytically stimulated 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 slag, 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.

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

[0007] 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.

[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 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.

[0013] Specifically, the particle size of the fluorite waste is less than 100 mesh.

[0014] 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.

[0015] Preferably, the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 10:1.5.

[0016] 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.

[0017] In some specific embodiments, the weight ratio of iron nitrate to cobalt nitrate in the 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.

[0018] Through experimental analysis, it can be known that the present application further improves the application performance of the photocatalytic mineralizer by controlling the weight ratio of iron nitrate to cobalt nitrate in the nitrate to be within the above range.

[0019] In a second aspect, the present application provides a method for preparing the cement raw material mineralizer having the above-mentioned photocatalytically stimulated mineralization effect, which 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, and dried to obtain the cement raw material mineralizer with photocatalytic excitation mineralization effect.

[0020] Preferably, the electrophoretic deposition voltage is 6-18V DC voltage, and the pH of the electrophoretic solution is 2-4.

[0021] In a third aspect, the present application provides a cement raw meal, which is prepared using the cement raw meal mineralizer having a photocatalytically stimulated mineralization effect.

[0022] 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.

[0023] In summary, the technical solution of this application has the following effects: 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.

[0024] 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

[0025] 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.

[0026] 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. Example Examples 1-9

[0027] Examples 1-9 respectively provide a cement raw material mineralizer having a photocatalytically stimulated mineralization effect and a preparation method thereof.

[0028] 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.

[0029] The preparation method of the cement raw material mineralizer having the photocatalytic excitation mineralization effect in the above embodiment is: Weigh the corresponding weight portions of the raw material components respectively, dissolve nitrate (composed of a mixture of ferric nitrate and cobalt nitrate in 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 adopts a 12V DC voltage, and the pH of the electrophoretic solution is 3; Fluorite waste residue and fly ash are added to the modified CdSe quantum dot-carbon nanotube composite structure solution, mixed evenly, and dried to obtain a cement raw material mineralizer with photocatalytic excitation mineralization effect.

[0030] Table 1 Amount of each component in the cement raw material mineralizer with photocatalytic mineralization effect in Examples 1-9 Examples 10-13

[0031] Examples 10-13 respectively provide a cement raw material mineralizer having a photocatalytically stimulated mineralization effect and a preparation method thereof.

[0032] The difference between the above embodiment and embodiment 2 is that the nitrate composition is different, as shown below.

[0033] In Example 10: the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 8:2 (ie 4:1).

[0034] In Example 11: the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 12:1.

[0035] In Example 12: the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 9:1.8.

[0036] In Example 13: the nitrate is composed of a mixture of iron nitrate and cobalt nitrate in a weight ratio of 11:1.2.

[0037] The types of other raw material components, the amounts of each raw material, and the preparation method process parameters in the above embodiment are the same as those in Example 2. Examples 14-17

[0038] Examples 14-17 respectively provide a cement raw material mineralizer having a photocatalytically stimulated mineralization effect and a preparation method thereof.

[0039] The difference between the above embodiment and embodiment 2 is that the electrophoretic deposition process parameters are different, as shown below.

[0040] In Example 14: the electrophoretic deposition voltage is 6V DC voltage, and the pH value of the electrophoretic solution is 4.

[0041] In Example 15: the electrophoretic deposition voltage is 18V DC voltage, and the pH value of the electrophoretic liquid is 2.

[0042] In Example 16: the electrophoretic deposition voltage is 9V DC voltage, and the pH of the electrophoretic solution is 3.5.

[0043] In Example 17: the electrophoretic deposition voltage is 15V DC, and the pH of the electrophoretic solution is 2.5.

[0044] The types of raw material components and the amounts of each raw material as well as other preparation method process parameters in the above embodiment are the same as those in Example 2. Comparative Example Comparative Examples 1-5

[0045] Comparative Examples 1-5 respectively provide a photocatalytic mineralizer and a preparation method thereof.

[0046] The difference between the comparative example and Example 2 is that the dosage of each component in the cement raw material mineralizer having a photocatalytic excitation mineralization effect is different, as shown in Table 2.

[0047] Table 2 The amount of each component in the cement raw material mineralizer with photocatalytic mineralization effect in Comparative Examples 1-5

[0048] The other process parameters in the above comparative example are the same as those in Example 2. Comparative Examples 6-7

[0049] Comparative Examples 6-7 respectively provide a cement raw material mineralizer with catalytic effect and a preparation method thereof.

[0050] The differences between the above comparative example and Example 2 are specifically as follows.

[0051] In Comparative Example 6: the nitrate is composed of a mixture of iron nitrate and potassium nitrate in a weight ratio of 10:1.5.

[0052] In Comparative Example 7: the nitrate is composed of a mixture of cobalt nitrate and iron nitrate in a weight ratio of 10:1.5.

[0053] The types of other raw material components, the amounts of each raw material, and other preparation method process parameters in the above comparative example are the same as those in Example 2. Comparative Example 8

[0054] Comparative Example 8 provides a mineralizer.

[0055] The mineralizer in this comparative example is fluorite waste slag. Performance testing

[0056] The high-efficiency photocatalytic mineralizer prepared by the embodiment and the comparative example was tested in a cement dry process production line. The raw material mill adopted a grinding process of a roller press + a powder selector. The amount of the mineralizer added was 0.1% of the total mass of the raw material. The standard coal consumption per ton of clinker, the clinker strength at 3d, 7d, and 28d, and the sulfur content of flue gas (mg / m 3 ) for testing.

[0057] Test results: as shown in Table 3.

[0058] Table 3 Performance test results of mineralizers in Examples 1-17 and Comparative Examples 1-8

[0059] By analyzing Table 3 and comparing the performance test results of the photocatalytic mineralizers in the embodiments and the 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 in the present application can act on fluorite waste slag and excite the mineralized components in the fluorite waste slag, thereby improving the mineralization effect of the fluorite waste slag.

[0060] By comparing the performance test results of the photocatalytic mineralizer in Examples 1-9 and Comparative Examples 4-5, it can be seen 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.

[0061] By comparing the performance test results of the photocatalytic mineralizer in Example 2 with those in Examples 10-13, it can be seen that the present application further improves the application performance of the photocatalytic mineralizer by controlling the weight ratio of iron nitrate to cobalt nitrate in nitrate to 9-11:1.2-1.8.

[0062] Although the present invention has been described in detail above with general descriptions and specific embodiments, it is obvious to those skilled in the art that some modifications or improvements may be made thereto based on the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A cement raw material mineralizer having a photocatalytic 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.

2. The cement raw material mineralizer with photocatalytic 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 cement raw material mineralizer with photocatalytic 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 cement raw material mineralizer with photocatalytic 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 cement raw material mineralizer with photocatalytic 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 cement raw material mineralizer with photocatalytic 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 method for preparing the cement raw material mineralizer having photocatalytic mineralization effect according to any one of claims 1 to 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 method for preparing the cement raw material mineralizer having photocatalytic 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 material, 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 method for preparing cement raw material 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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