Ecological maintenance type snow-melting agent and preparation method thereof
The complex co-crystallized from calcium magnesium acetate and ecological functional components solves the problem of soil stress caused by snow melting agents, achieving efficient snow melting and soil remediation, reducing costs, and conforming to the concept of green development.
Patent Information
- Application Number
- CN202511673431.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-14
- Publication Date
- 2026-01-16
AI Technical Summary
Existing snow-melting agents cause stress to the soil micro-ecology after snow melting, have a single function, cannot actively improve soil conditions, and are costly, have limited raw materials, and have insufficient environmental benefits.
A complex formed by co-crystallization of calcium magnesium acetate and ecological functional components is prepared by the synergistic use of agricultural and industrial waste. The calcium magnesium acetate is obtained by reacting calcium and magnesium-containing industrial solid waste with acetic acid solution from distillers' grains fermentation. The ecological functional components are compounded from biogas slurry concentrate and coal humic acid to form an ecologically protective snow melting agent.
It achieves efficient snow melting without corrosion, and can actively maintain and restore the soil micro-ecology, reduce costs, improve soil fertility and vegetation vitality, which is in line with the concept of green development.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of green chemistry and waste resource utilization technology, specifically relating to an ecological de-icing agent prepared from agricultural waste and industrial solid waste. This product has the characteristics of being chlorine-free, low-corrosion, biodegradable, and soil-improving. Background Technology
[0002] Winter road snow melting and ice removal are related to people's livelihood and traffic safety. While widely used chloride-based snow melting agents (such as sodium chloride) have immediate effects, their long-term harms are becoming increasingly prominent: (1) Severe corrosion of infrastructure: Chloride ions cause strong corrosion to public infrastructure such as roads, bridges, and vehicles, which greatly shortens their service life; (2) Persistent damage to the ecological environment: After snow melting, salts invade the soil, leading to compaction and salinization, which harms green plants and pollutes groundwater with runoff, thus disrupting the ecological balance; (3) Implicit transfer of social costs: Behind its low purchase price is the transfer of high environmental and social costs to the whole society, with the whole people "paying" for its long-term damage, which is not in line with the concept of green development.
[0003] CN118256193A discloses a method for preparing an environmentally friendly snow-melting agent using industrial solid waste. This method involves recycling industrial acetic acid waste liquid, acetic acid, calcium carbide slag, purification ash, and salt mud to prepare the environmentally friendly snow-melting agent. The calcium carbide slag, purification ash, salt mud, and acetic acid waste liquid in the raw materials are all recycled waste, promoting solid waste recycling, reducing disposal costs and environmental pollution. The prepared snow-melting agent has low cost, is chlorine-free, environmentally friendly, and has good snow-melting effect; the waste residue is properly treated, without causing secondary environmental pollution. The snow-melting agent has advantages such as good snow-melting effect (≥120% of sodium chloride's snow-melting capacity), low freezing point (≤-30℃), no corrosion to carbon steel, and low cost. It not only meets the needs of resource utilization of industrial solid waste but can also directly replace chloride-based snow-melting agents in terms of performance. However, it still has the following shortcomings: the snow-melting agent has a single function, only focusing on "harmlessness" (such as chlorine-free and low corrosion), failing to solve the stress on the soil micro-ecology caused by long-term use of snow-melting agents, and cannot achieve "beneficial" effects. Soil commonly suffers from problems such as compaction and reduced microbial activity after snowmelt, and currently no snow-melting agent can actively improve this situation. Summary of the Invention
[0004] The purpose of this invention is to provide a low-cost, high-performance, eco-friendly snow-melting agent and its preparation method. By co-utilizing agricultural and industrial waste, this snow-melting agent not only melts snow efficiently and without corrosion, but also actively maintains and repairs the soil micro-ecology, achieving a technological leap from "environmentally friendly" to "ecologically beneficial," and solving the problems of high cost, limited raw materials, and insufficient environmental benefits of existing snow-melting agent products.
[0005] The ecological maintenance-type snow melting agent provided by the present invention is a complex formed by the co-crystallization of calcium magnesium acetate and ecological functional components; based on the total mass of the raw materials forming the complex, it contains 85% to 95% calcium magnesium acetate and 5% to 15% ecological functional components; the ecological functional components are compounded from biogas slurry concentrate and coal humic acid at a mass ratio of 1:0.5 to 3.
[0006] Furthermore, based on the total mass of the raw materials forming the composite, the snow-melting agent preferably contains 88% to 92% calcium magnesium acetate and 8% to 12% ecological functional components.
[0007] Furthermore, the ecological functional component is preferably a mixture of biogas slurry concentrate and coal humic acid in a mass ratio of 1:1 to 2.
[0008] Furthermore, the calcium magnesium acetate is derived from the reaction product of calcium and magnesium-containing industrial solid waste and acetic acid solution obtained from the fermentation of distiller's grains.
[0009] The method for preparing the eco-friendly de-icing agent provided by this invention includes the following steps:
[0010] Step 1: The industrial solid waste containing calcium and magnesium is subjected to acid hydrolysis reaction with acetic acid solution. After the reaction, solid-liquid separation is performed, and the filtrate is collected to obtain calcium magnesium acetate solution.
[0011] Step 2: Separate the biogas slurry into solid and liquid components and concentrate it through a membrane to obtain biogas slurry concentrate; extract and purify the weathered coal to obtain coal humic acid; mix the two in a certain proportion to obtain the ecological functional component.
[0012] Step 3: The ecological functional components are compounded with calcium magnesium acetate solution at 40-60°C for 0.5-1.5 hours to allow the two to co-crystallize and form a complex; the compounded solution is then dried to obtain an ecological snow-melting agent.
[0013] Furthermore, in step 1 above, the calcium- and magnesium-containing industrial solid waste is selected from at least one of carbide slag, purified ash slag, magnesium slag, and salt mud.
[0014] Furthermore, in step 1 above, the acetic acid solution is an acetic acid solution with a mass concentration of 12% to 18% obtained by microbial fermentation of distiller's grains.
[0015] The beneficial effects of this invention are as follows:
[0016] 1. This invention utilizes fermented distiller's grains liquid to replace commercial acetic acid and reacts it with industrial solid waste containing calcium and magnesium (such as calcium carbide slag and magnesium slag) to prepare calcium magnesium acetate solution. It also combines agricultural waste (biogas slurry and weathered coal) as the main raw materials to achieve "waste treatment with waste" and reduce the overall cost by up to 60% compared with traditional calcium magnesium acetate.
[0017] 2. The de-icing agent of this invention is chloride-free, biodegradable, and has virtually no corrosion to carbon steel. It completely avoids the erosion and damage to roads, bridges, vehicles, and the surrounding environment caused by traditional chloride de-icing agents. Moreover, its snow-melting capacity can reach more than 120% of that of sodium chloride, ensuring high-efficiency snow and ice removal efficiency. It has both excellent snow-melting performance and outstanding environmental friendliness.
[0018] 3. This invention transforms a "snow-melting agent" into an "ecological maintenance agent," achieving a functional upgrade. After snow melting, the calcium and magnesium elements in the product can act as soil conditioners to enhance fertility, while the unique biogas slurry concentrate and humic acid can further stimulate plant vitality and promote ecological restoration. This ensures that after snow melting, it not only does not burden the environment but also has a positive maintenance effect on the soil and vegetation along the roadside.
[0019] 4. This invention successfully transforms various wastes into high-value resources, perfectly aligning with national policies of "zero-waste cities" and "circular economy." It provides a de-icing agent solution that integrates its own advantages, high efficiency, environmental friendliness, and ecological restoration, possessing profound social significance and broad market prospects. Detailed Implementation
[0020] The present invention will be described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited to these embodiments.
[0021] Example 1
[0022] Step 1: Preparation of calcium magnesium acetate solution
[0023] Distillers' grains collected from farmers were mixed with water and acetic acid bacteria at a ratio of 200g:1L:0.2g and fermented at 25℃ for 5 days to obtain an acetic acid solution with a mass concentration of 15%. Purified ash residue (its composition is shown in Table 1) was ground into powder with a particle size <1mm. The ground solid powder was mixed with water at a solid-liquid ratio of 1kg:5L and stirred evenly to obtain a calcium hydroxide magnesium slurry. The obtained calcium hydroxide magnesium slurry and the obtained acetic acid solution were mixed at a volume ratio of 1:3 and stirred at 60℃ for 20 minutes. After the reaction, solid-liquid separation was performed, and the filtrate was collected to obtain a calcium magnesium acetate solution (mass concentration of 33%±1%).
[0024] Table 1 Content of various substances in purified ash
[0025] Step 2: The biogas slurry is passed through a screen with a pore size of 1-5 mm to remove large suspended solids. Then, it is centrifuged at 5000 rpm for 5 minutes using a horizontal screw centrifuge to obtain solid biogas residue (typically with a moisture content of 65%-75%). Finally, the residue is passed through a permeate membrane with a pore size of <0.001 μm to obtain biogas slurry concentrate. Lump weathered coal is crushed to 60-100 mesh using a crusher. The resulting powder is mixed with a 50% sodium hydroxide aqueous solution at a solid-liquid mass ratio of 1:2 and stirred at 70°C for 1 hour. After the reaction is complete, the mixture is filtered. Hydrochloric acid is added to the filtrate to adjust the pH to 2-3. At this point, a large amount of humic acid will precipitate out. This precipitate is then filtered using a vacuum filter press. The filter cake is thoroughly washed with deionized water, and the washed wet humic acid is dried at 105°C to obtain solid coal humic acid. The biogas slurry concentrate and coal humic acid are mixed at a mass ratio of 1:1 to obtain the ecological functional component.
[0026] Step 3: Mix the obtained ecological functional component with the obtained calcium magnesium acetate solution at a mass ratio of 1:27, and compound at 50°C for 1 hour to allow the ecological functional component and calcium magnesium acetate to co-crystallize and form a complex; dry the compounded solution at 120°C to obtain an ecological maintenance-type de-icing agent. In the ecological maintenance-type de-icing agent, the mass content of calcium magnesium acetate is 90% and the mass content of the ecological functional component is 10%.
[0027] Comparative Example 1
[0028] In this comparative example, a calcium magnesium acetate solution was prepared according to the method of Example 1, and the calcium magnesium acetate solution was dried at 120°C and used as a de-icing agent.
[0029] Comparative Example 2
[0030] In this comparative example, calcium magnesium acetate solution and biogas slurry concentrate were prepared according to the method of Example 1. The calcium magnesium acetate solution and biogas slurry concentrate were mixed at a mass ratio of 27:1 and compounded at 50°C for 1 hour. The compounded solution was dried at 120°C to obtain the snow melting agent.
[0031] Comparative Example 3
[0032] In this comparative example, calcium magnesium acetate solution and coal humic acid were prepared according to the method of Example 1. The calcium magnesium acetate solution and coal humic acid were mixed at a mass ratio of 27:1 and compounded at 50°C for 1 hour. The compounded solution was dried at 120°C to obtain the de-icing agent.
[0033] Comparative Example 4
[0034] In this comparative example, a calcium magnesium acetate solution was prepared according to the method of Example 1. The calcium magnesium acetate solution was mixed with commercial sodium humate at a mass ratio of 27:1 and compounded at 50°C for 1 hour. The compounded solution was then dried at 120°C to obtain a snow melting agent.
[0035] Example 2
[0036] In step 2 of this embodiment, the biogas slurry concentrate and humic acid are mixed at a mass ratio of 1:2 to obtain the ecological functional component. The other steps are the same as in Example 1 to obtain the ecological maintenance type snow melting agent.
[0037] Example 3
[0038] In step 2 of this embodiment, the biogas slurry concentrate and coal humic acid are mixed at a mass ratio of 1:0.5 to obtain the ecological functional component. The other steps are the same as in Example 1 to obtain an ecologically maintaining de-icing agent.
[0039] Example 4
[0040] In step 2 of this embodiment, the biogas slurry concentrate and humic acid are mixed at a mass ratio of 1:3 to obtain the ecological functional component. The other steps are the same as in Example 1 to obtain the ecological maintenance type snow melting agent.
[0041] Example 5
[0042] In step 3 of this embodiment, the obtained ecological functional component and the obtained calcium magnesium acetate solution are mixed at a mass ratio of 1:17 and compounded at 50°C for 1 hour. The other steps are the same as in Example 1, resulting in an ecologically sound de-icing agent. The ecologically sound de-icing agent contains 85% calcium magnesium acetate and 15% ecological functional components by mass.
[0043] Example 6
[0044] In step 3 of this embodiment, the obtained ecological functional component and the obtained calcium magnesium acetate solution are mixed at a mass ratio of 1:57 and compounded at 50°C for 1 hour. The other steps are the same as in Example 1, resulting in an ecologically sound de-icing agent. In the ecologically sound de-icing agent, the mass content of calcium magnesium acetate is 95% and the mass content of the ecological functional component is 5%.
[0045] The de-icing agent products prepared in Examples 1-6 and Comparative Examples 1-4 were tested in accordance with GB / T23851-2017. The test results are shown in Table 2.
[0046] Table 2 Comparison of National Standard Test Results for Different Snow Melting Agents
[0047] Further testing was conducted on the impact of the snow-melting agent products prepared in Example 1 and Comparative Examples 1-4 on the ecological environment. The results are shown in Table 3.
[0048] Table 3. Impact Tests on the Ecological Environment of Different Snow Melting Agents
[0049] As can be seen from Tables 2 and 3 above, the snow-melting agents of Examples 1 to 6 of the present invention not only have a good snow-melting effect compared with the traditional calcium magnesium acetate (comparative example 1 snow-melting agent), but also significantly improve soil microbial diversity and plant seed germination rate. When biogas concentrate or coal humic acid is used alone in combination with calcium magnesium acetate, the improvement on soil and plants is not obvious (comparative examples 2 and 3). Biogas concentrate can provide plants with the nutrients necessary for growth, and coal humic acid can improve soil microbial activity and stimulate their function. Only when both are used in combination with calcium magnesium acetate can they exert great advantages. Although commercial sodium humate can also achieve certain effects, its high cost makes it difficult to circulate in the market. This invention utilizes agricultural and industrial waste in a synergistic manner. The combination of biogas slurry concentrate and coal humic acid produces a synergistic effect, breaking through the raw material and cost bottlenecks of existing snow-melting agents. The product is significantly superior to existing technologies in terms of snow-melting performance, environmental benefits, and economic efficiency. Most importantly, it improves soil conservation and vegetation growth, and has good overall application prospects.
Claims
1. An ecologically sustainable deicing agent, characterized in that: The snow-melting agent is a complex formed by co-crystallization of calcium-magnesium acetate and an ecological functional component; the complex contains 85-95% of calcium-magnesium acetate and 5-15% of the ecological functional component based on the total mass of the raw materials for forming the complex; the ecological functional component is formed by compounding a biogas slurry concentrate and coal humic acid at a mass ratio of 1:0.5-3.
2. The ecologically friendly deicing agent of claim 1, wherein: The complex contains 88-92% of calcium-magnesium acetate and 8-12% of the ecological functional component based on the total mass of the raw materials for forming the complex.
3. Ecocare de-icing salt according to claim 1 or 2, characterized in that: The ecological functional component is formed by compounding a biogas slurry concentrate and coal humic acid at a mass ratio of 1:1-2.
4. The ecocare deicing agent of claim 1 or 2, wherein: The calcium-magnesium acetate is derived from the reaction product of calcium- and magnesium-containing industrial solid waste and an acetic acid solution obtained by fermentation of vinasse.
5. A method of preparing the ecologically friendly deicing agent according to claim 1, characterized by: The preparation method comprises the following steps: Step 1: performing acidolysis reaction of calcium- and magnesium-containing industrial solid waste and an acetic acid solution, and then performing solid-liquid separation to collect the filtrate, i.e. to obtain a calcium-magnesium acetate solution; Step 2: performing solid-liquid separation and membrane concentration on biogas slurry to obtain a biogas slurry concentrate; and performing extraction and purification on weathered coal to obtain coal humic acid; mixing the two at a certain proportion to obtain an ecological functional component; Step 3: compounding the ecological functional component and the calcium-magnesium acetate solution at 40-60℃ for 0.5-1.5 hours to make them co-crystallize to form a complex; and drying the compounded solution to obtain an ecological maintenance-type snow-melting agent.
6. The method of preparing an ecologically friendly deicing agent according to claim 5, characterized in that: In Step 1, the calcium- and magnesium-containing industrial solid waste is at least one selected from carbide slag, purification ash, magnesium slag and salt sludge.
7. The method of claim 5, wherein the method further comprises: In Step 1, the acetic acid solution is an acetic acid solution obtained by microbial fermentation of vinasse, and the mass concentration of the acetic acid solution is 12-18%.