Preparation method of ecological environment-friendly snow-melting agent
By reacting amino acid fermentation waste liquid with melamine under the action of a catalyst, a granular eco-friendly snow melting agent is prepared, which solves the problem of damage to plants and high cost of existing snow melting agents, and achieves low-cost, environmentally friendly and safe snow melting. Effect.
Patent Information
- Application Number
- CN202411444836.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-16
- Publication Date
- 2025-01-21
AI Technical Summary
Existing snow melting agents cause salt stress, leaf damage and root damage to landscaping plants, and are costly to produce and costly.
After the amino acid fermentation waste liquid is anaerobic and diluted, it reacts with melamine under the action of catalyst to form a neutral solution, and the granular ecological and environmentally friendly snow melting agent is obtained through concentrated, granular, and crushed.
This method not only reduces the cost of raw materials, but also has good degradation performance, does not cause damage to plants, and can provide nitrogen fertilizer for soil.
Smart Images
Figure CN119331570A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of garden maintenance, and in particular to a method for preparing an eco-friendly snow-melting agent. Background Art
[0002] The main ingredients of deicing agents are usually potassium chloride or other salts. Although they are very effective in removing ice and snow on roads, if snow water containing a large amount of deicing agents is piled up or accumulated in green belts, it will have some adverse effects on landscape plants:
[0003] Salt stress: The salt in the de-icing agent will enter the soil, increase the salinity of the soil, make it difficult for plants to absorb water and nutrients, and thus cause the plants to die.
[0004] Leaf damage: If de-icing agents come into direct contact with plant leaves, they may cause leaf burns or wilting.
[0005] Root damage: In a high-salt environment, the root system of plants will be damaged, affecting their ability to absorb water and nutrients.
[0006] In order to reduce the impact of de-icing agents on plants, the following measures can be taken:
[0007] Proper storage: Avoid piling snow containing snow-melting agents directly in green belts, or choose to store it far away from plants.
[0008] Clean up promptly: After using snow-melting agents, clean up the residues on roads and green belts as soon as possible.
[0009] Rinse plants: If the de-icing agent has come into contact with plants, rinse them with clean water to reduce the impact of salt.
[0010] Improve soil: Soil that has been contaminated by salt can be improved by adding organic matter to reduce its salinity.
[0011] In addition, compared with traditional deicing agents such as potassium chloride and calcium chloride, calcium magnesium acetate deicing agent is a green and environmentally friendly substance that will not harm the environment and human health. However, its disadvantage is that its production cost is relatively high, resulting in its relatively high cost.
[0012] Based on this, the present invention is proposed. Summary of the invention
[0013] In view of the shortcomings of the prior art, the present invention provides a method for preparing an eco-friendly snow-melting agent, and the technical scheme thereof is as follows:
[0014] A method for preparing an eco-friendly snow-melting agent comprises the following steps:
[0015] Step 1, subjecting the amino acid fermentation waste liquid to anaerobic fermentation for 3 to 5 days to obtain anaerobic fermentation liquid;
[0016] Step 2, adding water to the anaerobic fermentation liquid to dilute it, to obtain an anaerobic fermentation dilution liquid;
[0017] Step 3, reacting the anaerobic fermentation dilution with melamine under the action of a catalyst at 110-120° C. for at least 6 hours, and after the reaction, adding a pH adjuster to the product to adjust the pH value of the product to 7±0.2 to obtain a neutral solution;
[0018] Step 4: Concentrate, granulate and crush the neutral liquid to obtain a granular eco-friendly snow-melting agent.
[0019] As a further solution of the present invention, the solid content of the anaerobic fermentation dilution liquid is 12-15%.
[0020] As a further embodiment of the present invention, the mass ratio of the anaerobic fermentation dilution liquid, melamine and catalyst is 100:(7-8):0.3.
[0021] As a further embodiment of the present invention, the pH adjuster is at least one of potassium bicarbonate, dipotassium hydrogen phosphate, potassium carbonate, potassium dihydrogen phosphate, citric acid, tartaric acid, oxalic acid and phosphoric acid.
[0022] As a further solution of the present invention, the catalyst is a CuO&ZIF-8 composite material.
[0023] As a further solution of the present invention, the preparation method of the CuO & ZIF-8 composite material comprises the following steps:
[0024] Zinc acetate is dissolved in methanol to prepare a zinc acetate methanol solution, 2-methylimidazole is dissolved in methanol to prepare a 2-methylimidazole methanol solution, CuO powder is poured into the zinc acetate methanol solution, and then the 2-methylimidazole methanol solution is added, ultrasonic dispersion is performed for 3 to 6 hours, and after the ultrasonic dispersion is completed, the mixture is allowed to stand for 24 to 48 hours, and filtered. The filter residue is rinsed with deionized water and methanol for 3 to 5 times, and then dried at 65 to 75° C. to obtain the CuO&ZIF-8 composite material.
[0025] The mass ratio of zinc acetate to 2-methylimidazole is 5:(10-12). The concentration of the zinc acetate methanol solution is 25-30 g / L, and the concentration of the zinc acetate methanol solution is 50-65 g / L. The particle size of the CuO powder is less than or equal to 5.8 μm.
[0026] In the present invention, firstly, the main raw material source of the present invention is amino acid fermentation waste liquid. The amino acid fermentation waste liquid undergoes anaerobic fermentation to generate short-chain organic acids and alcohols including propionic acid, lactic acid, acetic acid, butyric acid, valeric acid, etc., and a portion of melamine self-assembles with the above-mentioned organic acids, residual amino acids, etc. through hydrogen bonds, and the generated melamine salt and a small amount of amide-containing organic matter generated under the action of a catalyst are added. The above-mentioned products are finally mixed into a viscous, system-stable viscous substance according to their respective specific proportions; the viscous substance is subjected to pH adjustment to obtain a neutral liquid.
[0027] In the present invention, the eco-friendly snow-melting agent was found in a visible light degradation test to have an amide-containing organic matter content in the soil reduced to less than 100 ppm after 5 days of degradation under visible light irradiation, while other amino acid residues, melamine salts, etc. could also be effectively reduced, and could even provide fertilizer for the soil.
[0028] This invention uses the fermentation waste liquid produced by amino acid fermentation as the main raw material, undergoes secondary anaerobic fermentation and uses catalyst molecules for self-assembly to ultimately obtain an organic snow-melting agent with ecological restoration function.
[0029] Compared with the prior art, the beneficial effects of the present invention are:
[0030] 1. The preparation method of the eco-friendly snow-melting agent of the present invention mainly utilizes amino acid fermentation waste liquid as the main raw material source, uses less melamine and catalyst, and has extremely low raw material cost.
[0031] 2. It has good snow-melting performance. It is not only degradable, but also can provide a certain amount of nitrogen fertilizer for the soil. It is a green, ecological and environmentally friendly substance with low impact on the environment and will not cause damage to plants. It is very suitable for snow melting and de-icing on municipal roads with a large number of green belts, and has high promotion and use value. BRIEF DESCRIPTION OF THE DRAWINGS
[0032] Figure 1 This is a curve diagram of the reaction temperature and x of the anaerobic fermentation dilution and melamine. DETAILED DESCRIPTION
[0033] The present invention is described in detail below in conjunction with specific embodiments. The embodiments described below are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present invention.
[0034] Example 1
[0035] 1. The amino acid fermentation waste liquid is subjected to anaerobic fermentation for 5 days to obtain anaerobic fermentation liquid.
[0036] 2. Add water to the anaerobic fermentation liquid to dilute it to obtain an anaerobic fermentation dilution liquid; the solid content of the anaerobic fermentation dilution liquid is 12%.
[0037] 3. The anaerobic fermentation dilution and melamine are reacted at 110° C. for at least 6 hours under the action of a catalyst. After the reaction is completed, a pH regulator is added to the product (viscous substance) to adjust the pH value of the product to 7±0.2 to obtain a neutral solution; wherein the mass ratio of the anaerobic fermentation dilution, melamine and catalyst is 100:7:0.3. The pH regulator is at least one of potassium bicarbonate, dipotassium hydrogen phosphate, potassium carbonate, potassium dihydrogen phosphate, citric acid, tartaric acid, oxalic acid and phosphoric acid.
[0038] 4. Concentrate, granulate and crush the neutral liquid to obtain a granular snow-melting agent.
[0039] The catalyst is a CuO & ZIF-8 composite material. The preparation method of the CuO & ZIF-8 composite material comprises the following steps:
[0040] Zinc acetate is dissolved in methanol to prepare a zinc acetate methanol solution, 2-methylimidazole is dissolved in methanol to prepare a 2-methylimidazole methanol solution, CuO powder is poured into the zinc acetate methanol solution, and then the 2-methylimidazole methanol solution is added, ultrasonic dispersion is performed for 3 hours, and after the ultrasonic dispersion is completed, the mixture is allowed to stand for 24 hours, and filtered. The filter residue is rinsed with deionized water and methanol for 3 to 5 times, and then dried at 65° C. to obtain the CuO&ZIF-8 composite material.
[0041] The mass ratio of zinc acetate to 2-methylimidazole is 5:10. The concentration of the zinc acetate methanol solution is 25 g / L, and the concentration of the zinc acetate methanol solution is 50 g / L. The particle size of the CuO powder is less than or equal to 5.8 μm.
[0042] Example 2
[0043] 1. The amino acid fermentation waste liquid is subjected to anaerobic fermentation for 3 days to obtain anaerobic fermentation liquid.
[0044] 2. Add water to the anaerobic fermentation liquid to dilute it to obtain an anaerobic fermentation dilution liquid; the solid content of the anaerobic fermentation dilution liquid is 13%.
[0045] 3. The anaerobic fermentation dilution and melamine are reacted at 115° C. for at least 6 hours under the action of a catalyst. After the reaction is completed, a pH regulator is added to the product (viscous substance) to adjust the pH value of the product to 7±0.2 to obtain a neutral solution; wherein the mass ratio of the anaerobic fermentation dilution, melamine and catalyst is 100:7.3:0.3. The pH regulator is at least one of potassium bicarbonate, dipotassium hydrogen phosphate, potassium carbonate, potassium dihydrogen phosphate, citric acid, tartaric acid, oxalic acid and phosphoric acid.
[0046] 4. Concentrate, granulate and crush the neutral liquid to obtain a granular snow-melting agent.
[0047] The catalyst is a CuO & ZIF-8 composite material. The preparation method of the CuO & ZIF-8 composite material comprises the following steps:
[0048] Zinc acetate is dissolved in methanol to prepare a zinc acetate methanol solution, 2-methylimidazole is dissolved in methanol to prepare a 2-methylimidazole methanol solution, CuO powder is poured into the zinc acetate methanol solution, and then the 2-methylimidazole methanol solution is added, ultrasonic dispersion is performed for 4 hours, and after the ultrasonication is completed, it is allowed to stand for 24 hours, filtered, and the filter residue is rinsed with deionized water and methanol for 3 to 5 times, and then dried at 70°C to obtain the CuO&ZIF-8 composite material.
[0049] The mass ratio of zinc acetate to 2-methylimidazole is 5:11. The concentration of the zinc acetate methanol solution is 25 g / L, and the concentration of the zinc acetate methanol solution is 50 g / L. The particle size of the CuO powder is less than or equal to 5.8 μm.
[0050] Example 3
[0051] 1. The amino acid fermentation waste liquid is subjected to anaerobic fermentation for 3 days to obtain anaerobic fermentation liquid.
[0052] 2. Add water to the anaerobic fermentation liquid to dilute it to obtain an anaerobic fermentation dilution liquid; the solid content of the anaerobic fermentation dilution liquid is 15%.
[0053] 3. The anaerobic fermentation dilution and melamine are reacted at 110-120° C. for at least 6 hours under the action of a catalyst. After the reaction is completed, a pH regulator is added to the product (viscous substance) to adjust the pH value of the product to 7±0.2 to obtain a neutral solution; wherein the mass ratio of the anaerobic fermentation dilution, melamine and catalyst is 100:8:0.3. The pH regulator is at least one of potassium bicarbonate, dipotassium hydrogen phosphate, potassium carbonate, potassium dihydrogen phosphate, citric acid, tartaric acid, oxalic acid and phosphoric acid.
[0054] 4. Concentrate, granulate and crush the neutral liquid to obtain a granular snow-melting agent.
[0055] The catalyst is a CuO & ZIF-8 composite material. The preparation method of the CuO & ZIF-8 composite material comprises the following steps:
[0056] Zinc acetate is dissolved in methanol to prepare a zinc acetate methanol solution, 2-methylimidazole is dissolved in methanol to prepare a 2-methylimidazole methanol solution, CuO powder is poured into the zinc acetate methanol solution, and then the 2-methylimidazole methanol solution is added, ultrasonic dispersion is performed for 6 hours, and after the ultrasonication is completed, it is allowed to stand for 48 hours, filtered, and the filter residue is rinsed with deionized water and methanol for 3 to 5 times, and then dried at 75°C to obtain the CuO&ZIF-8 composite material.
[0057] The mass ratio of zinc acetate to 2-methylimidazole is 5:12. The concentration of the zinc acetate methanol solution is 30 g / L, and the concentration of the zinc acetate methanol solution is 65 g / L. The particle size of the CuO powder is less than or equal to 5.8 μm.
[0058] Comparative Example 1
[0059] The only difference between this example and Example 1 is that, in this example, melamine is replaced by urea of equal mass, and the rest remains unchanged.
[0060] Comparative Example 2
[0061] The only difference between this example and Example 1 is that in this example, the CuO&ZIF-8 composite material is replaced by a molecular sieve of equal mass, and the rest remains unchanged.
[0062] Comparative Example 3
[0063] The only difference between this example and Example 1 is that in this example, the CuO&ZIF-8 composite material is replaced by TiO2&ZIF-8, wherein the only difference between TiO2&ZIF-8 and CuO&ZIF-8 is that CuO powder is replaced by TiO2 powder.
[0064] Comparative Example 4
[0065] The only difference between this example and Example 1 is that in this example, the CuO&ZIF-8 composite material is replaced by ZIF-8 (ZIF-8 metal organic framework material purchased from Xi'an Qiyue Biotechnology Co., Ltd.), and the rest remains unchanged.
[0066] Comparative Example 5
[0067] The only difference between this example and Example 1 is that in this example, the CuO&ZIF-8 composite material is replaced by CuO, and the rest remains unchanged.
[0068] 《De-icing Agent Performance Characterization Test》
[0069] The deicing agents in Examples 1 to 3 and Comparative Examples 1 to 5 were stirred with water to prepare a sample solution with a solid content of 18%, and a sodium chloride solution with a mass fraction of 18% was prepared as a reference agent. The freezing point, relative deicing and ice melting ability, and relative damage rate of lawn grass seeds of the deicing agents were tested according to the standard "DB11 T161-2012 Deicing Agents". The test results are shown in Table 1.
[0070] Table 1
[0071] Freezing point(℃) Relative snow and ice melting capacity Relative damage rate to turfgrass seeds Example 1 -12.7 Type I 15.6％ Example 2 -13.1 Type I 17.1％ Example 3 -11.2 Type I 18.5％ Comparative Example 1 / Less than 90% of the de-icing capacity of calcium chloride dihydrate / Comparative Example 2 / Less than 90% of the de-icing capacity of calcium chloride dihydrate / Comparative Example 3 / Less than 90% of the de-icing capacity of calcium chloride dihydrate / Comparative Example 4 / Less than 90% of the de-icing capacity of calcium chloride dihydrate / Comparative Example 5 / Less than 90% of the de-icing capacity of calcium chloride dihydrate / Reference agent -14.3 / 81.7％
[0072] The eco-friendly snow-melting agent prepared by the present invention has a significantly lower effect on the germination rate of plant seeds than the reference agent (potassium chloride), indicating that it causes less salinization and damage to the soil and plants.
[0073] 2. "Stability test of sticky substances"
[0074] y is the initial lactam content of the viscous material.
[0075] After stirring the viscous substance for 15 minutes, centrifuge it at 3000 r / min for 10 minutes and let it stand for 5 minutes. Use a separatory funnel to take the upper and lower liquid layers respectively, and use high performance liquid chromatography (HPLC) to measure the amide content in the upper and lower liquid layers, x = difference in amide content between the upper and lower liquid layers / amide content in the lower liquid layer.
[0076] The larger the x, the worse the stability of the viscous material. On the one hand, once the viscous material is left for a long time during the production process, it is easy to cause uneven content of the upper and lower layers, resulting in a large difference in the uniformity of the content of the deicing salt. On the other hand, it means that the reaction in step 3 is not fully reacted (or even does not react), which significantly affects the quality of the subsequent finished deicing agent.
[0077] The viscous substances in Examples 1 to 3 and Comparative Examples 1 to 5 were tested, and the results are shown in Table 2:
[0078] Table 2
[0079] x(％) y(％) Example 1 3.6 1.15 Example 2 4.3 1.23 Example 3 4.7 1.07 Comparative Example 1 / 0.09 Comparative Example 2 / 0.31 Comparative Example 3 25.5 0.63 Comparative Example 4 / 0.39 Comparative Example 5 / 0.28
[0080] Referring to the preparation process of Example 1, when the anaerobic fermentation dilution liquid reacts with melamine under the action of a catalyst at temperatures of 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, and 130°C, the corresponding curve graph is shown in FIG. Figure 1 , it can be seen that x is preferably 110-120°C, more preferably 115°C.
[0081] In addition, it should be understood that those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment may also be appropriately combined to form other implementation methods that can be understood by those skilled in the art.
Claims
1. A method for preparing an eco-friendly snow-melting agent, characterized in that: The following steps are involved: Step 1, subjecting the amino acid fermentation waste liquid to anaerobic fermentation for 3 to 5 days to obtain anaerobic fermentation liquid; Step 2, adding water to the anaerobic fermentation liquid to dilute it, to obtain an anaerobic fermentation dilution liquid; Step 3, reacting the anaerobic fermentation dilution with melamine under the action of a catalyst at 110-120° C. for at least 6 hours, and after the reaction, adding a pH adjuster to the product to adjust the pH value of the product to 7±0.2 to obtain a neutral solution; Step 4: Concentrate, granulate and crush the neutral liquid to obtain a granular eco-friendly snow-melting agent.
2. The method for preparing an eco-friendly snow-melting agent according to claim 1, characterized in that: The solid content of the anaerobic fermentation dilution liquid is 12-15%.
3. The method for preparing an eco-friendly snow-melting agent according to claim 1, characterized in that: The mass ratio of the anaerobic fermentation dilution liquid, melamine and catalyst is 100:(7-8):0.
3.
4. The method for preparing an eco-friendly snow-melting agent according to claim 1, characterized in that: The pH adjuster is at least one of potassium bicarbonate, dipotassium hydrogen phosphate, potassium carbonate, potassium dihydrogen phosphate, citric acid, tartaric acid, oxalic acid and phosphoric acid.
5. The method for preparing an eco-friendly snow-melting agent according to claim 1, characterized in that: The catalyst is a CuO&ZIF-8 composite material.
6. The method for preparing an eco-friendly snow-melting agent according to claim 5, characterized in that: The preparation method of the CuO & ZIF-8 composite material comprises the following steps: Zinc acetate is dissolved in methanol to prepare a zinc acetate methanol solution, 2-methylimidazole is dissolved in methanol to prepare a 2-methylimidazole methanol solution, CuO powder is poured into the zinc acetate methanol solution, and then the 2-methylimidazole methanol solution is added, ultrasonic dispersion is performed for 3 to 6 hours, and after the ultrasonic dispersion is completed, the mixture is allowed to stand for 24 to 48 hours, filtered, and the filter residue is rinsed with deionized water and methanol for 3 to 5 times, and then dried to obtain the CuO&ZIF-8 composite material.
7. The method for preparing an eco-friendly snow-melting agent according to claim 6, characterized in that: The mass ratio of the zinc acetate to 2-methylimidazole is 5:(10-12).
8. The method for preparing an eco-friendly snow-melting agent according to claim 6, characterized in that: The concentration of the zinc acetate methanol solution is 25-30 g / L, and the concentration of the zinc acetate methanol solution is 50-65 g / L.
9. The method for preparing an eco-friendly snow-melting agent according to claim 6, characterized in that: The particle size of the CuO powder is less than or equal to 5.8 μm.
10. The method for preparing an eco-friendly snow-melting agent according to claim 6, characterized in that: The drying temperature is 65-75℃.