A coal-saving and energy-reducing cement mineralizer and its preparation method
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUILIN HUAYUE ENVIRONMENTAL PROTECTION TECH CO LTD
- Filing Date
- 2023-11-29
- Publication Date
- 2026-06-30
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of cement manufacturing technology, and in particular to a coal-saving and energy-reducing cement mineralizer and its preparation method. Background Technology
[0002] Currently, domestic cement technology is becoming increasingly mature, production line construction scale is expanding, and market competition is intensifying. Cement companies are increasingly using additives to further reduce manufacturing costs, improve cement production and quality, and enhance their market competitiveness to adapt to the commercialization of concrete.
[0003] Cement mineralizers are cement production admixtures derived from new forms of industrial applications. They play a vital role in improving production efficiency and reducing energy consumption in the cement industry, bringing tangible benefits to cement enterprises. Currently, my country's cement mineralizer production has gradually moved away from a situation of single-product offerings and inferior performance. Especially after foreign mineralizer manufacturers entered the Chinese cement market, Chinese manufacturers were prompted to develop products to meet different market demands, resulting in a significant improvement in the quality of Chinese mineralizer products. However, overall, most Chinese mineralizer manufacturers still suffer from simple production equipment, outdated testing methods, limited product variety, and excessive levels of harmful substances, severely restricting their market competitiveness. In recent years, research on cement mineralizers has received high attention from universities, research institutes, and technology development companies, yielding numerous achievements. In line with industry development, the development and research of mineralizers is essential.
[0004] However, the commonly used fluorite and gypsum mineralizers are constrained by environmental problems caused by the volatilization of fluorine and sulfur at high temperatures. Therefore, this application aims to develop a new type of mineralizer to prevent the pollution of waste gas from harmful components at the source. Summary of the Invention
[0005] In view of the above, it is necessary to provide a method for preparing a coal-saving and energy-reducing cement mineralizer. This invention, through reasonable formula design and product compounding, utilizes the synergistic effect between various substances to produce a green, environmentally friendly, and pollution-free special cement mineralizer.
[0006] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0007] A method for preparing a coal-saving and energy-reducing cement mineralizer, wherein the cement mineralizer comprises the following components by weight: 10-15 parts of polyol amine, 5-10 parts of calcium fluoride, 5-10 parts of organic acid salt, 8-15 parts of acryloyl oxyammonium salt, 8-15 parts of tartaric acid, 5-10 parts of molasses, 5 parts of nano-hydrated calcium silicate, 5-10 parts of treatment agent and 20-54 parts of water.
[0008] Furthermore, the cement mineralizer comprises, by weight, the following components: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water.
[0009] Furthermore, the calcium fluoride is nano-calcium fluoride.
[0010] Further, the treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2-3:3-4:1:1-2:30-40 and stirred at a temperature of 50-60℃ for 3-4 hours to obtain the treatment agent.
[0011] Further, the method includes the following steps: (1) putting nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heating to 100-110℃, stirring and mixing to obtain mixture A; (2) while stirring, adding water to mixture A to obtain mixture B; (3) adding polyol amine to mixture B, mixing thoroughly to obtain the cement mineralizer.
[0012] Furthermore, after adding water in step (2), the reaction is stirred for another 20-30 minutes.
[0013] Furthermore, in step (3), before adding the polyol amine, the temperature of mixture B is lowered to 20-30°C.
[0014] The acryloyloxyammonium salt includes one or any combination of two of acryloyloxyethyltrimethylammonium chloride and methacryloyloxyethyltrimethylammonium chloride.
[0015] The present invention has at least the following beneficial effects:
[0016] 1. This application, through reasonable formula design and product compounding, utilizes the synergistic effect between various substances to produce a green, environmentally friendly, and pollution-free special cement mineralizer. It has advantages such as low production cost, simple and convenient production process, good clinker reduction effect, low sensitivity to changes in cement raw materials, good strength retention effect, and strong adaptability.
[0017] 2. This application develops a novel cement mineralizer to prevent and control air pollution from harmful components at the source. In the preparation process, nano-calcium fluoride, organic acid salts, acryloyl oxyammonium salt, tartaric acid, molasses, and nano-hydrated calcium silicate are first mixed and stirred at high temperature. Then, water is added and stirred. Finally, after cooling, polyol amine is added to obtain the final product. By adding the mineralizer to the cement, the reaction bonds in the reaction process are induced to break to a certain extent, thereby accelerating the reaction rate. At the same time, after experimental verification, it was found that the obtained cement exhibits good compressive strength and durability.
[0018] 3. This application also adds a treatment agent to the cement mineralizer. In practical operation, the applicant found that after adding the cement mineralizer of this application, the compressive strength and durability of the cement are both good. However, the cement mineralizer prepared in this application, when applied to cement, makes it brittle at low temperatures and prone to cracking. Therefore, it is not suitable for low-temperature environments such as the snowy north. To solve this problem, this application adds a treatment agent. Experiments have shown that the addition of the treatment agent can improve the cement's freeze-thaw resistance. The light calcium carbonate can reduce the porosity of the entire system, and sodium salicylate can effectively fix water molecules. The straw ash forms a large number of microbubbles. When the cement's operating temperature is lower than the predetermined value, the water in the bubble freezes and is squeezed into the bubble, isolating it from other strength-enhancing components and ensuring that the cement is not affected by the frozen water. Through the treatment agent of this application, the cement can maintain its strength even at low temperatures. Detailed Implementation
[0019] All features disclosed in this specification, or all steps in all disclosed methods or processes, may be combined in any way, except for mutually exclusive features and / or steps.
[0020] Unless otherwise stated, each feature disclosed in this specification (including any appended claims and abstract) is merely one example of a series of equivalent or similar features.
[0021] Example 1:
[0022] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 10 parts polyol amine, 5 parts calcium fluoride, 5 parts organic acid salt, 8 parts acryloyl oxyammonium salt, 8 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 5 parts treatment agent, and 20 parts water. The calcium fluoride is nano-calcium fluoride.
[0023] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:1:30 and stirred at 50°C for 3 hours to obtain the treatment agent.
[0024] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0025] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 100°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 20 minutes after adding water to obtain mixture B; (3) Lower the temperature of mixture B to 20°C, then add polyol amine to mixture B, mix thoroughly, and the cement mineralizer can be obtained.
[0026] Example 2:
[0027] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water. The calcium fluoride is nano-calcium fluoride.
[0028] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:2:35 and stirred at 55°C for 3.5 hours to obtain the treatment agent.
[0029] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0030] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 105°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 25 minutes after adding water to obtain mixture B; (3) Lower the temperature of mixture B to 25°C, then add polyol amine to mixture B, mix thoroughly, and the cement mineralizer can be obtained.
[0031] Example 3:
[0032] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 15 parts polyol amine, 10 parts calcium fluoride, 10 parts organic acid salt, 15 parts acryloyl oxyammonium salt, 15 parts tartaric acid, 10 parts molasses, 5 parts nano-hydrated calcium silicate, 5 parts treatment agent, and 54 parts water. The calcium fluoride is nano-calcium fluoride.
[0033] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:3:4:1:2:40 and stirred at a temperature of 60°C for 4 hours to obtain the treatment agent.
[0034] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0035] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 110°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 30 minutes after adding water to obtain mixture B; (3) Lower the temperature of mixture B to 30°C, then add polyol amine to mixture B, mix thoroughly, and the cement mineralizer can be obtained.
[0036] Comparative Example 1:
[0037] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 14 parts polyol amine, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water.
[0038] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:2:35 and stirred at 55°C for 3.5 hours to obtain the treatment agent.
[0039] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0040] (1) Place organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 105°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 25 minutes after adding water to obtain mixture B; (3) Lower the temperature of mixture B to 25°C, then add polyol amine to mixture B and mix thoroughly to obtain the cement mineralizer.
[0041] Comparative Example 2:
[0042] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water. The calcium fluoride is nano-calcium fluoride.
[0043] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:2:35 and stirred at 55°C for 3.5 hours to obtain the treatment agent.
[0044] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0045] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 105°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 25 minutes after adding water to obtain mixture B; (3) Without cooling, directly add polyol amine to mixture B, mix thoroughly, and the cement mineralizer can be obtained.
[0046] Comparative Example 3:
[0047] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water. The calcium fluoride is nano-calcium fluoride.
[0048] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:2:35 and stirred at 55°C for 3.5 hours to obtain the treatment agent.
[0049] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0050] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses, polyol amine and nano-hydrated calcium silicate into a mixer, slowly heat to 105°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 25 minutes after adding water to obtain the cement mineralizer.
[0051] Comparative Example 4:
[0052] This embodiment provides a coal-saving and energy-reducing cement mineralizer, which comprises the following components by weight: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water. The calcium fluoride is nano-calcium fluoride.
[0053] The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2:3:1:2:35 and stirred at 55°C for 3.5 hours to obtain the treatment agent.
[0054] This embodiment also provides a method for preparing the above-mentioned cement mineralizer, including the following steps:
[0055] (1) Place nano-calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate into a mixer, slowly heat to 105°C, stir and mix to obtain mixture A; (2) While stirring, add water to mixture A, and continue stirring and reacting for 25 minutes after adding water to obtain mixture B; (3) Lower the temperature of mixture B to 25°C, then add polyol amine to mixture B, mix thoroughly, and the cement mineralizer can be obtained.
[0056] Experimental example:
[0057] To illustrate the practical value of this application, the described cement mineralizer was applied to the production of cement clinker, with the mineralizer accounting for 0.2% of the weight of the cement raw meal. After grinding the raw meal, it was calcined in a vertical shaft kiln according to conventional cement production methods to obtain cement clinker. The free calcium oxide, physical properties, and standard coal consumption of the obtained cement clinker were recorded, as shown in Table 1.
[0058] Table 1
[0059]
[0060] According to the test results in Table 1, the cement clinker prepared by adding the cement mineralizer obtained by the method described in Examples 1-3 of this application has good durability and low standard coal consumption, thus saving costs. However, Comparative Example 3, which directly mixes all raw materials, has poor durability. Comparative Example 2, which did not lower the system temperature before adding the polyol amine, has poor compressive strength and poor durability. Although the preparation process was simply adjusted, unexpected results occurred. Comparative Examples 1 and 4, which only removed one of the raw materials, had a significant decrease in compressive strength. This shows that the cement mineralizer of this application has a great influence on the product by both the combination of raw materials and the preparation method. The mineralizer obtained by the method of this application is not only widely available and inexpensive, but also has no adverse effect on the performance of cement, especially its durability, and has good application prospects.
[0061] Furthermore, the applicant further tested the frost resistance of the cement, comparing the frost resistance of the following groups with that of the cement in Example 2. Similarly, as in the aforementioned tests, the mineralizer was applied in the production of the cement, and the groups are as follows:
[0062] Group 1: The mineralizer described in Example 2, applied in cement;
[0063] Group 2: Remove the treatment agent, otherwise the same as Group 1;
[0064] Group 3: Remove sodium salicylate from the treatment agent; other methods are the same as Group 1.
[0065] Group 4: Remove straw ash from the treatment agent; other methods are the same as Group 1.
[0066] Group 5: Replace straw ash with tea saponin, otherwise the same as Group 1;
[0067] Group 6: The mineralizer in Comparative Example 3, with the treatment agent component removed.
[0068] The cements prepared in the above groups were subjected to the following tests: Ten pieces of 28-day clinker cement of the same specifications were selected and placed in a cold storage at -35℃ for 3 months. After that, the appearance of each group was observed and the presence of cracks and breakage was recorded. After being taken out and restored to (25±2)℃, the compressive strength and flexural strength were tested and the average values were recorded. The results are shown in Table 2:
[0069] Table 2
[0070]
[0071] As shown in Table 2, the treatment agent of this application enables cement products to be used normally at low temperatures without cracking due to low temperatures, and its compressive strength and flexural strength are basically unaffected. As shown in Group 6, the mineralizer prepared by the method of this application is more prone to cracking. Therefore, adding a treatment agent is a necessary means. The raw materials of the treatment agent of this application are mutually compatible and cannot be separated, which helps to improve the cold resistance of cement and make its application more widespread.
[0072] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are specific and detailed, they should not be construed as limiting the scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these modifications and improvements all fall within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the appended claims.
Claims
1. A cement mineralizer for saving coal and reducing energy consumption, characterized in that, The cement mineralizer comprises the following components by weight: 10-15 parts of polyol amine, 5-10 parts of calcium fluoride, 5-10 parts of organic acid salt, 8-15 parts of acryloyl oxyammonium salt, 8-15 parts of tartaric acid, 5-10 parts of molasses, 5 parts of nano-hydrated calcium silicate, 5-10 parts of treatment agent and 20-54 parts of water. The treatment agent is obtained by the following method: raw materials consisting of the following parts by weight: metakaolin, sodium salicylate, straw ash, light calcium carbonate, sodium carboxymethyl cellulose and water are mixed in a mass ratio of 1:2-3:3-4:1:1-2:30-40 and stirred at a temperature of 50-60℃ for 3-4 hours to obtain the treatment agent.
2. The cement mineralizer according to claim 1, characterized in that, The cement mineralizer comprises, by weight, the following components: 14 parts polyol amine, 9 parts calcium fluoride, 6 parts organic acid salt, 14 parts acryloyl oxyammonium salt, 9 parts tartaric acid, 5 parts molasses, 5 parts nano-hydrated calcium silicate, 7 parts treatment agent, and 38 parts water.
3. The cement mineralizer according to claim 1, characterized in that, The calcium fluoride is nano-sized calcium fluoride.
4. A method for preparing the cement mineralizer according to any one of claims 1-3, characterized in that, The method includes the following steps: (1) Calcium fluoride, organic acid salt, acryloyl oxyammonium salt, tartaric acid, treatment agent, molasses and nano-hydrated calcium silicate are put into a mixer, the temperature is slowly raised to 100-110℃, and the mixture is stirred to obtain mixture A; (2) While stirring, water is added to mixture A to obtain mixture B; (3) Polyol amine is added to mixture B and mixed thoroughly to obtain the cement mineralizer.
5. The method according to claim 4, characterized in that, After adding water in step (2), continue stirring and reacting for 20-30 minutes.
6. The method according to claim 4, characterized in that, In step (3), before adding the polyol amine, the temperature of mixture B is lowered to 20-30°C.