Plant-based recoverable road snow-melting agent and preparation method thereof

Abstract

The invention provides a plant-based recyclable road snow-melting agent and a preparation method thereof, and belongs to the field of composite road snow-melting materials. The plant-based recoverable road snow-melting agent is prepared from ice-melting salt and a high-molecular polymer, the high-molecular polymer is formed by cross-linking polymerization of plant-based cellulose, organic modified clay mineral inorganic components, acrylic acid and acrylamide derivatives. The snow-melting agent provided by the invention is prepared by extracting plant cellulose from agricultural solid waste as a raw material, has excellent snow-melting capacity, is small in environmental corrosion, can absorb ice water after ice melting to form light white gel, can be dried and crushed after being used for reuse, and is still stable in performance when being repeatedly used, so that the snow-melting agent is suitable for industrial production. And the requirements of green and low-carbon development are met.

Description

Technical Field

[0001] This invention belongs to the field of composite road snow melting materials; in particular, it relates to a plant-based recyclable road snow melting agent and its preparation method. Background Technology

[0002] In the field of environmental engineering, the use of de-icing agents is crucial for road safety and smooth traffic flow, especially in northern my country where large-scale low-temperature rainfall and snowfall in winter cause road icing, severely impacting commuting efficiency. However, while traditional chloride-based de-icing agents (such as NaCl and MgCl2) are inexpensive and effective at melting snow, they are highly corrosive to the environment and infrastructure. Long-term use of chloride-based de-icing agents leads to soil salinization, water pollution, and corrosion damage to infrastructure such as bridges and roads, posing a persistent threat to regional ecological security and the maintenance of public assets. In recent years, environmentally friendly de-icing agents, represented by acetates, have developed rapidly, but their usage costs are high. Furthermore, both chloride-based and acetate-based de-icing agents are single-use products and cannot be reused, resulting in resource waste. Meanwhile, agricultural solid waste, such as bagasse and coconut shells, is directly dumped or incinerated, resulting in low resource utilization rates. Therefore, developing a novel environmentally friendly and recyclable plant-based de-icing agent has become an urgent research need. Summary of the Invention

[0003] In order to overcome the technical problems of existing de-icing agents corroding the environment and infrastructure, one objective of this invention is to provide a plant-based recyclable road de-icing agent, and another objective of this invention is to provide a method for preparing a plant-based recyclable road de-icing agent.

[0004] This invention relates to a plant-based recyclable road de-icing agent composed of de-icing salt and a high-molecular polymer. The high-molecular polymer is cross-linked and polymerized from plant-based cellulose, organically modified clay mineral inorganic components, acrylic acid, and acrylamide derivatives. This de-icing agent has excellent de-icing ability and low environmental corrosivity. After de-icing, it absorbs ice water to form a light white gel. After use, it can be dried and pulverized for reuse, and its performance remains stable even after repeated use. It is environmentally friendly, recyclable, and cost-effective, meeting the requirements of green and low-carbon development.

[0005] This invention is achieved through the following technical solution:

[0006] The first objective of this invention is to provide a plant-based recyclable road de-icing agent, composed of de-icing salt and a high molecular polymer;

[0007] The polymer is formed by cross-linking and polymerization of plant-based cellulose, organically modified clay mineral inorganic components, acrylic acid, and acrylamide derivatives;

[0008] When the de-icing salt is inorganic, the polymer is coated on the outer surface of the de-icing salt;

[0009] When the de-icing salt is an organic de-icing salt, the de-icing salt is linked to the polymer.

[0010] The plant-based cellulose content is 5-30 wt% of the acrylic acid mass; the content of the organically modified clay mineral inorganic components is 2-10 wt% of the acrylic acid mass; the amount of ice-melting salt is 150-400 wt% of the acrylic acid mass; and the amount of acrylamide derivative is 20-40 wt% of the acrylic acid mass.

[0011] Preferably, the plant-based cellulose is bagasse cellulose, coconut shell cellulose, peanut shell cellulose, or rice straw cellulose;

[0012] The organically modified clay mineral inorganic components are attapulgite, halloysite, bentonite, kaolin, or laterite.

[0013] The acrylamide derivative is acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N-isopropylacrylamide, or N-hydroxyethylacrylamide;

[0014] The inorganic de-icing salt is calcium chloride, sodium chloride, or magnesium chloride;

[0015] The organic de-icing salt is potassium acetate or sodium acetate.

[0016] A second objective of this invention is to provide a method for preparing a plant-based recyclable road de-icing agent, comprising the following steps:

[0017] Step S1: Prepare plant-based cellulose;

[0018] Step S2: Preparation of organically modified clay mineral inorganic components:

[0019] The inorganic components of clay minerals are dissolved in an organic solvent, and then a modifier is added to obtain a mixture. The mixture is heated to 60-80℃, and the pH value of the mixture is adjusted to 8-10 with NaOH solution. The mixture is stirred continuously for 3-5 hours, cooled, filtered to remove impurities, washed, filtered by suction, dried at 50-80℃ to constant weight, pulverized, and sieved to obtain the organically modified inorganic components of clay minerals.

[0020] Step S3: Preparation of plant-based recyclable road de-icing agent:

[0021] S3.1 Preparation of mixed solution B: After neutralizing acrylic acid, acrylic acid, acrylamide derivative and ice-melting salt are mixed under the action of crosslinking agent and initiator to form mixed solution B;

[0022] S3.2 Dissolve the organically modified clay mineral inorganic components and plant-based cellulose in water, introduce inert gas, heat to 50-80℃ and stir continuously for 30-60 minutes to obtain a uniformly mixed emulsion.

[0023] S3.3. Slowly add mixed solution B to the emulsion and react for 2-4 hours to obtain crude product; dry the crude product at 50-80℃ to constant weight, crush and sieve to obtain plant-based recyclable road de-icing agent.

[0024] Preferably, step S1 specifically includes the following steps:

[0025] S1.1 Powdering: Boil the plant-based raw material for 30-60 minutes, dry it, then mechanically crush and grind it into powder;

[0026] S1.2 Alkaline hydrolysis: Weigh the powder and pour it into an alkaline solution of NaOH and H2O2. React at 80-100℃ for 2-4 hours with stirring. Cool and filter, wash with water until neutral, filter again, and then dry at 50-70℃ to constant weight to obtain alkaline hydrolysis product A1.

[0027] S1.3 Acid hydrolysis: Weigh the product A1 after alkaline hydrolysis and pour it into H2SO4 solution. Heat to 80-100℃ and stir continuously for 3-5 hours. Filter out impurities, and dry by vacuum filtration to obtain acid hydrolysis product A2.

[0028] S1.4 Bleaching: Weigh the acid hydrolysis product A2 and pour it into a sodium chlorite solution. Adjust the pH of the solution to 4-6 with glacial acetic acid. Stir the reaction at 70-90℃ for 3-6 hours. Wash with water until the pH is neutral. After drying, white plant-based cellulose is obtained.

[0029] Preferably, in step S1, the plant base is bagasse, coconut shell, peanut shell, or rice straw; the clay mineral inorganic component is attapulgite, halloysite, bentonite, kaolin, or laterite.

[0030] Preferably, in step S1, the mixed solution of NaOH and H2O2 during the alkaline hydrolysis process...

[0031] Preferably, the mass fraction of NaOH is 3-10 wt%, the mass fraction of H2O2 is 0.5-1 wt%, and the solid-liquid ratio is 1:10-1:20;

[0032] Preferably, the volume fraction of H2SO4 during the acid hydrolysis process is 1-3% v / v, and the solid-liquid ratio is 1:10-1:20;

[0033] Preferably, the volume fraction of sodium chlorite in the bleaching process is 1-5 wt%, and the solid-liquid ratio is 1:10-1:20.

[0034] Preferably, in step S2, the modifier is KH-550, KH-560, KH-570, KH-590, KH-602 or KH-792;

[0035] Preferably, the solid-liquid ratio of the inorganic component to the modifier is 1:0.8-1:1.5.

[0036] Preferably, in step S3, the content of plant-based cellulose is 5-30 wt% of the acrylic acid content, the content of organically modified clay mineral inorganic components is 2-10 wt% of the acrylic acid content, the amount of acrylamide derivative is 20-40 wt% of the acrylic acid content, the amount of crosslinking agent is 0.10-0.25 wt% of the acrylic acid content, the amount of initiator is 0.4-0.12 wt% of the acrylic acid content, and the amount of ice-melting salt is 150-400 wt% of the acrylic acid content.

[0037] Preferably, in step S3, acrylic acid is neutralized with NaOH to a degree of neutralization of 50-80%.

[0038] Preferably, in step S3, the acrylamide derivative is acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N-isopropylacrylamide, or N-hydroxyethylacrylamide;

[0039] The crosslinking agent is N,N'-methylenebisacrylamide;

[0040] The initiator is ammonium persulfate or potassium persulfate;

[0041] The de-icing salt is calcium chloride, sodium chloride, magnesium chloride, potassium acetate, or sodium acetate.

[0042] The present invention has the following advantages:

[0043] 1. The snow melting agent prepared by the present invention has a better snow melting ability than the ice melting ability of commercially available snow melting agents, and its low-temperature ice melting ability is stronger, which can meet the snow melting needs in low-temperature environments and ensure driving safety in winter.

[0044] 2. The snow melting agent prepared by the present invention has excellent repeated snow melting ability. When repeated five times, the snow melting ability is only slightly lower than that of commercially available snow melting agents, and in the other four times, it is higher than that of commercially available snow melting agents.

[0045] 3. The de-icing agent prepared by this invention has a low environmental corrosion rate, which greatly reduces the degree of corrosion of bridge metal components and automobile chassis, making it an environmentally friendly de-icing agent.

[0046] 4. The de-icing agent prepared by this invention uses agricultural solid waste such as bagasse, coconut shell, peanut shell and rice straw as raw materials. While ensuring the excellent de-icing properties of the de-icing agent, it also promotes the high-value utilization of agricultural solid waste.

[0047] 5. The plant-based recyclable road de-icing agent prepared by this invention has a simple preparation process, meets the requirements for ice melting efficiency, and can be recycled and reused after drying and pulverizing, which meets the requirements of green and low-carbon development. Attached Figure Description

[0048] Figure 1 A physical image of the plant-based recyclable road de-icing agent prepared according to this invention;

[0049] Figure 2 Scanning electron microscope image of the plant-based recyclable road de-icing agent prepared according to the present invention;

[0050] Figure 3 XRD pattern of the plant-based recyclable road de-icing agent prepared according to the present invention;

[0051] Figure 4 Thermogravimetric analysis of the preparation of the plant-based recyclable road de-icing agent of this invention;

[0052] Figure 5 The figure shows a comparison of the ice-melting effects of the plant-based recyclable road de-icing agent prepared in this invention and commercially available de-icing agents.

[0053] Figure 6 A comparison chart showing the ice-melting performance of the plant-based recyclable road de-icing agent prepared in this invention and commercially available de-icing agents;

[0054] Figure 7 The diagram shows the repeated ice-melting performance of the plant-based recyclable road de-icing agent prepared according to this invention. Detailed Implementation

[0055] The present invention will now be described in detail with reference to specific embodiments. It should be noted that the following embodiments are merely further illustrations of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.

[0056] This invention provides a plant-based recyclable road de-icing agent, which is composed of de-icing salt and a high molecular polymer.

[0057] Preferably, the polymer is formed by cross-linking and polymerization of plant-based cellulose, organically modified clay mineral inorganic components, acrylic acid, and acrylamide derivatives.

[0058] Preferably, when the de-icing salt is inorganic, a polymer is coated on the outer surface of the de-icing salt to form a core-shell-like structure.

[0059] Preferably, when the de-icing salt is an organic de-icing salt, the de-icing salt is linked to the polymer.

[0060] The plant-based cellulose content is 5-30 wt% of the acrylic acid mass; the content of the organically modified clay mineral inorganic components is 2-10 wt% of the acrylic acid mass; the amount of ice-melting salt is 150-400 wt% of the acrylic acid mass; and the amount of acrylamide derivative is 20-40 wt% of the acrylic acid mass.

[0061] Preferably, the plant-based cellulose is bagasse cellulose, coconut shell cellulose, peanut shell cellulose, or rice straw cellulose.

[0062] Preferably, the inorganic components of the organically modified clay minerals are attapulgite, halloysite, bentonite, kaolin, or laterite.

[0063] Preferably, the acrylamide derivative is acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N-isopropylacrylamide, or N-hydroxyethylacrylamide.

[0064] Preferably, the inorganic de-icing salt is calcium chloride, sodium chloride, or magnesium chloride.

[0065] Preferably, the organic de-icing salt is potassium acetate or sodium acetate.

[0066] The above-mentioned technical solutions of the present invention will be described in detail below with specific embodiments.

[0067] It should be noted that, unless otherwise specified, the chemical reagents and pharmaceuticals used in the following embodiments are all commercially available products in the field.

[0068] It should be noted that, unless otherwise specified, the operations used in the following embodiments are all conventional operations in the art. Unless otherwise specified, the test methods used are all conventional and known standard test methods in the art.

[0069] Example 1

[0070] This embodiment relates to a method for preparing a plant-based recyclable road de-icing agent, the specific steps of which are as follows:

[0071] (1) Powdering: After drying the coconut shell, peel off the coconut shell shreds, boil for 30 minutes to remove soluble impurities, dry in an oven and grind into powder for later use.

[0072] (2) Alkaline hydrolysis: Weigh coconut shell powder and pour it into a mixed alkaline solution of 5wt% NaOH and 0.8wt% H2O2, with a solid-liquid ratio of 1:20. Add the solution to a flask and assemble a condenser. React at 80℃ with stirring for 3 hours. After the reaction is complete, wait for it to cool to room temperature, wash it several times with water until the pH value is neutral, filter it, and dry the filter cake in an oven to obtain the alkaline-treated product A1.

[0073] (3) Acid hydrolysis: Weigh product A1 and pour it into 1% v / v H2SO4 solution at a solid-liquid ratio of 1:10 to achieve hydrolysis of amorphous cellulose. React at 80℃ for 1 h, filter to remove trace minerals, and dry to obtain acid hydrolysis product A2.

[0074] (4) Bleaching: Weigh A2 and pour it into a 2wt% sodium chlorite solution with a solid-liquid ratio of 1:20. Adjust the pH of the solution to about 5 with glacial acetic acid. Stir the reaction magnetically at 90°C for 4 hours. Wash with water until the pH is neutral. After drying, obtain the white product coconut cellulose.

[0075] (5) Measure 5g of attapulgite, 50mL of anhydrous ethanol and 2.5mL of KH-550 and pour them into a 150mL flask. Heat to 80℃ and stir magnetically for 1h to obtain a suspension. Then adjust the pH of the suspension to about 8 with NaOH solution and react for 3h. After the reaction is complete, wash with distilled water until neutral, filter, dry and grind to obtain organically modified attapulgite, that is, organically modified clay mineral inorganic component.

[0076] (6) Measure and mix 0.1 mol of acrylic acid with a neutralization degree of 80%, 2.88 g of 2-acrylamide-2-methyl-1-propanesulfonic acid (acrylamide derivative), 0.0086 g of N,N-methylene-2-acrylamide, 0.0072 g of ammonium persulfate and 21.6 g of calcium chloride to obtain a mixed solution;

[0077] (7) Weigh 1.44g of coconut cellulose, 0.432g of organically modified attapulgite, and 30mL of water into a flask, purge with nitrogen, heat to 70°C, and magnetically stir for 30min to ensure uniform dispersion of coconut cellulose and attapulgite in the solution. Then, slowly add the mixed solution dropwise into the flask and maintain the temperature at 70°C for 3h. After the reaction, place the pale white product in anhydrous ethanol for 1h, then place it in an oven until the weight no longer changes. Finally, pulverize to obtain a recyclable de-icing agent of approximately 100 mesh coconut cellulose / attapulgite-calcium chloride-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid), i.e., a plant-based recyclable road de-icing agent. In this embodiment, coconut cellulose / attapulgite-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid) is a high molecular weight polymer that coats the outer surface of calcium chloride, utilizing the network structure of the high molecular weight polymer to coat the calcium chloride.

[0078] Example 2

[0079] This embodiment relates to a method for preparing a plant-based recyclable road de-icing agent, the specific steps of which are as follows:

[0080] (1) Powdering: After drying the bagasse, boil it for 40 minutes to remove soluble impurities, dry it in an oven, and then grind it into powder for later use.

[0081] (2) Alkaline hydrolysis: Weigh bagasse powder and add it to a mixed alkaline solution of 7wt% NaOH and 1wt% H2O2 at a solid-liquid ratio of 1:20. Add the solution to a flask and assemble a condenser. React at 80℃ with stirring for 3 hours. After the reaction is complete, allow it to cool to room temperature and wash it several times with water until the pH value is neutral. Filter the solution and dry the filter cake in an oven to obtain the alkaline-treated product A1.

[0082] (3) Acid hydrolysis: Weigh product A1 and pour it into 2% v / v H2SO4 solution with a solid-liquid ratio of 1:20. React at 90℃ for 2 hours to hydrolyze amorphous cellulose. Filter to remove trace minerals and dry to obtain acid hydrolysis product A2.

[0083] (4) Bleaching: Weigh A2 and pour it into a 3wt% sodium chlorite solution with a solid-liquid ratio of 1:20. Adjust the pH of the solution to about 6 with glacial acetic acid. Stir the reaction magnetically at 80°C for 4 hours. Wash with water until the pH is neutral. After drying, obtain the white product bagasse cellulose.

[0084] (5) Measure 5g halloysite, 50mL anhydrous ethanol and 2.5mL KH-570 and pour them into a 150mL flask. Heat to 70℃ and stir magnetically for 1h to obtain a suspension. Then adjust the pH of the suspension to about 9 with NaOH solution and react for 3h. After the reaction is complete, wash with distilled water until neutral, filter, dry and grind to obtain organically modified halloysite, that is, organically modified clay mineral inorganic component.

[0085] (6) Weigh 1.44g of bagasse cellulose, 0.576g of organically modified halloysite and 30mL of distilled water into a flask, purge with nitrogen, heat to 80℃, and magnetically stir for 30min to ensure that the bagasse cellulose and halloysite are evenly dispersed in the solution. Then, slowly add the mixed solution of 0.1mol of 70% neutralized acrylic acid, 2.52g of 2-acrylamide-2-methyl-1-propanesulfonic acid (acrylamide derivative), 0.0072g of N,N-methylene-2-acrylamide, 0.0086g of ammonium persulfate and 18g of magnesium chloride into the flask, and maintain the temperature at 70℃ to continue the reaction for 3h. After the reaction was complete, the pale white product was placed in anhydrous ethanol for 1 hour, then placed in an oven until its weight no longer changed. Finally, it was pulverized to obtain a recyclable de-icing agent of approximately 100 mesh, namely, a plant-based recyclable road de-icing agent, consisting of bagasse cellulose / halothite-magnesium chloride-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid). In this embodiment, the polymer formed by bagasse cellulose / halothite-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid) coats the outer surface of magnesium chloride.

[0086] Example 3

[0087] This embodiment relates to a method for preparing a plant-based recyclable road de-icing agent, the specific steps of which are as follows:

[0088] (1) Boil peanut shells for 30 minutes to remove soluble impurities, dry them in an oven, and grind them into powder for later use. Weigh the peanut shell powder and pour it into a mixed solution of 8wt% NaOH and 1wt% H2O2 with a solid-liquid ratio of 1:20. Add the solution to a flask and assemble a condenser. React at 90℃ with stirring for 2 hours. After the reaction is complete, cool to room temperature and wash the mixture several times with distilled water until the pH value is neutral. Filter the mixture and dry the filter cake in an oven to obtain the alkali-treated product A1. Weigh product A1 and pour it into a 5% v / v H2SO4 solution with a solid-liquid ratio of 1:20. React at 80℃ for 2 hours to remove trace minerals and hydrolyze amorphous cellulose. After drying, obtain the acid-hydrolyzed product A2. Weigh A2 and pour it into a 5 wt% sodium chlorite solution with a solid-liquid ratio of 1:20. Adjust the pH of the solution to about 5 with glacial acetic acid. Stir the reaction magnetically at 90°C for 3 hours. Wash with distilled water until the pH is neutral. After drying, obtain the white product coconut husk cellulose.

[0089] (2) Measure 5g of kaolin, 50mL of anhydrous ethanol and 2.5mL of KH-792 and pour them into a 150mL flask. Heat to 60℃ and stir magnetically for 1h to obtain a suspension. Then adjust the pH of the suspension to about 9 with NaOH solution and react for 3h. After the reaction is complete, wash with distilled water until neutral, filter, dry and grind to obtain organically modified attapulgite, that is, organically modified clay mineral inorganic component.

[0090] (3) Weigh 1.8g of peanut shell cellulose, 0.72g of organic modified kaolin and 30mL of distilled water into a flask, purge with nitrogen, heat to 70℃, and magnetically stir for 30min to ensure that the coconut shell cellulose and attapulgite are evenly dispersed in the solution. Then, slowly add the mixture of 0.1mol of 65% neutralized acrylic acid, 2.88g of 2-acrylamide-2-methyl-1-propanesulfonic acid (acrylamide derivative), 0.0086g of N,N-methylene-2-acrylamide, 0.0072g of potassium persulfate and 14.4g of potassium acetate into the flask, and maintain the temperature at 70℃ to continue the reaction for 3h. After the reaction, the pale white product was placed in anhydrous ethanol for 1 hour, then placed in an oven until its weight no longer changed. Finally, it was pulverized to obtain a recyclable de-icing agent of approximately 100 mesh (peanut cellulose / kaolin-potassium acetate-poly(acrylo-2-acrylamido-2-methyl-1-propanesulfonic acid)), i.e., a plant-based recyclable road de-icing agent. In this embodiment, the polymer formed by peanut cellulose / kaolin-poly(acrylo-2-acrylamido-2-methyl-1-propanesulfonic acid) is linked to potassium acetate.

[0091] In the above embodiments, plant-based cellulose can be replaced with rice straw cellulose. The organically modified clay mineral inorganic components can be replaced with bentonite or laterite. Acrylamide derivatives can be replaced with acrylamide, N-isopropylacrylamide, or N-hydroxyethylacrylamide; inorganic de-icing salt can be replaced with sodium chloride, and organic de-icing salt can be replaced with sodium acetate.

[0092] In the above embodiments, the content of plant-based cellulose can be arbitrarily replaced within 5-30 wt% of the acrylic acid mass; the content of the organically modified clay mineral inorganic components can be arbitrarily replaced within 2-10 wt% of the acrylic acid mass; the amount of ice-melting salt can be arbitrarily replaced within 150-400 wt% of the acrylic acid mass; the amount of acrylamide derivative can be arbitrarily replaced within 20-40 wt% of the acrylic acid mass; the amount of crosslinking agent can be arbitrarily replaced within 0.10-0.25 wt% of the acrylic acid mass; and the amount of initiator can be arbitrarily replaced within 0.4-0.12 wt% of the acrylic acid mass.

[0093] The performance of the plant-based recyclable road de-icing agent prepared in Example 1 was further tested.

[0094] Performance Test 1

[0095] The plant-based recyclable road de-icing agent prepared in Example 1 Figure 1 The image shown is a physical picture of a recyclable de-icing agent made of coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid).

[0096] Performance Test 2

[0097] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to scanning electron microscopy tests at different magnifications, such as... Figure 2 As shown, the plant-based recyclable road de-icing agent exhibits a microsphere shape, with the coconut shell cellulose / attapulgite-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid) network structure coating calcium chloride to form a core-shell-like structure.

[0098] Performance Test 3

[0099] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to XRD testing, such as... Figure 3As shown, the characteristic peaks of calcium chloride are present in the XRD curves of plant-based recyclable road de-icing agents, but the peak intensity and peak area are reduced. This is because coconut cellulose / attapulgite-calcium chloride-poly(acrylo-2-acrylamido-2-methyl-1-propanesulfonic acid) coats the surface of calcium chloride, forming an organic film. This results in a decrease in the intensity of the characteristic peaks in coconut cellulose / attapulgite-calcium chloride-poly(acrylo-2-acrylamido-2-methyl-1-propanesulfonic acid), indicating that the tighter the network structure, the stronger the repeated de-icing performance.

[0100] Performance Test 4

[0101] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to TG testing, such as... Figure 4 As shown, calcium chloride and coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) exhibit similar curve distributions, both roughly divided into three stages, corresponding to temperature ranges of 30-226℃, 226-775℃, 775-1000℃ and 30℃-144℃, 144-446℃, 446-1000℃, respectively. In the first range, water evaporates. Since calcium chloride contains six molecules of water of crystallization, at 30-80℃, calcium chloride hexahydrate first decomposes into calcium chloride dihydrate. As the temperature rises to 80-117℃, calcium chloride dihydrate continues to decompose to form calcium chloride monohydrate. When the temperature is between 117-226℃, calcium chloride monohydrate finally loses all its water of crystallization to form anhydrous calcium chloride. Therefore, the TG images show three water loss ranges. Anhydrous calcium chloride shows no significant decrease in mass between 226-775℃, but once the temperature exceeds 775℃, it begins to decompose into CaO and Cl2, leading to a rapid decrease in mass. In coconut cellulose / attapulgite-calcium chloride-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid), the first stage of water loss is relatively gradual due to factors such as aqueous solution polymerization. In the second stage, the decrease in mass of coconut cellulose / attapulgite-calcium chloride-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid) is caused by the destruction and decomposition of small molecules such as oligomers and branches on the polymer chains in coconut cellulose / attapulgite-calcium chloride-poly(acryloyl-2-acrylamido-2-methyl-1-propanesulfonic acid). Within the temperature range of 446-775℃, both the branches and main chains within the coconut husk cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) network structure are damaged. Furthermore, at temperatures above 775℃, calcium chloride begins to decompose, generating CaO and Cl2, leading to further quality degradation. Since plant-based recyclable de-icing agents require drying after use, TG testing indicates that they exhibit good thermal stability, ensuring that the material's performance does not significantly degrade after repeated drying processes.

[0102] Performance Test 5

[0103] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to de-icing performance testing, and a comprehensive comparison was made with a commercially available group (using a commercially available environmentally friendly de-icing agent, the main component of which is sodium acetate). Figure 5 As shown, (a) and (b) are images of ice melting tests on petri dishes, concrete specimens, and Marshall specimens, respectively, of commercially available de-icing agents and recyclable de-icing agents made from coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid). It can be seen that commercially available de-icing agents dissolve in ice water after melting, and the effective de-icing components cannot be recovered. However, coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) forms a light white gel after melting, absorbs the melted ice water, floats on the surface of the ice, and can be recovered, dried, crushed, and recycled. It is this characteristic that makes coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) recyclable and reusable.

[0104] Figure 6 The graph shows a comparison of the ice-melting performance of coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) and commercially available de-icing agents (commercially available environmentally friendly de-icing agents with sodium acetate as the main component were used in the experiment) at different temperatures. It can be seen that the ice-melting performance of coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) is far superior to that of commercially available de-icing agents. Table 1 below shows the comparison of the ice melting amount of commercially available de-icing agents and coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) for 30 minutes at -5℃, -10℃, -15℃ and -20℃.

[0105] Table 1 Comparison of ice melting capacity between commercially available snow melting agents and Example 1 under the same conditions.

[0106]

[0107] Table 1 clearly shows that the ice-melting ability of coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) is superior to that of commercially available de-icing agents. Furthermore, the difference between the two increases as the ambient temperature decreases, indicating that coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) has a strong low-temperature ice-melting ability, which can meet the needs of snow melting in low-temperature environments and ensure driving safety in winter.

[0108] Performance Test 6

[0109] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to repeated ice-melting performance tests, see [link to example]. Figure 7 As shown, the ice-melting amounts after five 30-minute cycles at -10℃ were 6.0 g / g, 6.11 g / g, 5.94 g / g, 5.76 g / g, and 5.32 g / g, respectively. The ice-melting efficiency did not change significantly in the first three cycles, but began to decrease in the fourth cycle. This may be due to the damage to the resin network and the precipitation of some calcium chloride from the structure as the number of cycles increased. However, coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) still showed good repeated ice-melting performance, and the ice-melting efficiency in the fifth cycle reached 88% of the initial state. Meanwhile, commercially available de-icing agents showed a de-icing performance of 5.45 g / g after 30 minutes at -10℃, while coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) still showed 5.32 g / g after five repeated de-icing cycles. The material's performance after five repeated de-icing cycles was only slightly lower than that of commercially available de-icing agents, proving that coconut shell cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) has excellent repeated de-icing advantages.

[0110] Performance Test 7

[0111] The plant-based recyclable road de-icing agent prepared in Example 1 was subjected to corrosion performance testing, and a comprehensive comparison was made with commercially available products. The corrosion resistance of the de-icing agent to metal was tested using the weight loss method.

[0112] At room temperature, iron nails of the same type were polished, washed with water, and then dried in a vacuum drying oven at 70℃ for 12 hours. They were then weighed, accurate to 1 mg. To reduce experimental error, the weight of the four test nails was kept consistent during polishing of the upper surface. Four 100 mL beakers were labeled G1, G2, G3, and G4. G1 was filled with 100 mL of distilled water as a control group. G2 was added with 100 mL of 5 wt% commercially available de-icing agent solution. G3 and G4 were each added with 100 mL of 5 wt% coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) de-icing agent solution. The mixtures were stirred thoroughly and allowed to stand for 30 minutes to obtain the four test media: G1, G2, G3, and G4. Group G4 underwent filtration to remove excess water, retaining only the absorbed coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid). The other three groups were left untreated. The treated iron nails were inserted into the G1, G2, G3, and G4 test media, ensuring the insertion depth was the same. They were left to stand for 16 hours, then exposed to the atmosphere for 8 hours, and this process was repeated three times. After the test, the nails were derusted, cleaned, dried again, and weighed. The corrosion rate was calculated, as shown in Table 2.

[0113] Table 2 shows that the corrosion rates of iron nails in groups G1, G2, G3, and G4, with corresponding mass loss rates of 0.1667%, 0.3750%, 0.2083%, and 0.3333%, respectively, were the lowest in distilled water. Comparing G2, G3, and G4, it can be found that regardless of whether the test solution is poured out, the mass loss rate of the coconut cellulose / attapulgite-calcium chloride-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) test group was lower than that of the commercially available group. Calcium chloride precipitates slowly from the coconut cellulose / attapulgite-poly(acrylic acid-2-acrylamido-2-methyl-1-propanesulfonic acid) resin structure during the test, and its corrosive ability to metals is relatively weak. This is beneficial for reducing the corrosion of bridge metal components and automobile chassis by de-icing agents, making it an environmentally friendly de-icing agent.

[0114] Table 2 shows the corrosion rates of distilled water, commercially available de-icing agent, and the de-icing agent from Example 1.

[0115]

[0116] In summary, the plant-based recyclable road de-icing agent prepared by this invention has a simple preparation process, meets the requirements for de-icing efficiency, and can be recycled and reused after drying and pulverizing, thus meeting the requirements for green and low-carbon development.

[0117] It should be noted that the above performance tests were all based on the plant-based recyclable road de-icing agent prepared in the examples. When the performance tests were also conducted on the plant-based recyclable road de-icing agents obtained in Examples 2, 3, or the replacements, they all showed the same or similar performance as in Example 1, with stronger low-temperature ice melting ability and repeated snow melting ability, and lower environmental corrosion rate. It is an environmentally friendly and recyclable road de-icing agent.

[0118] The specific embodiments of the present invention have been described above. It should be understood that the present invention is not limited to the specific embodiments described above, and those skilled in the art can make various modifications or variations within the scope of the claims, which do not affect the essence of the present invention.

Claims

1. A plant-based recyclable road de-icing agent, characterized in that: Composed of ice-melting salt and high molecular polymers; The polymer is formed by cross-linking and polymerization of plant-based cellulose, organically modified clay mineral inorganic components, acrylic acid, and acrylamide derivatives; When the de-icing salt is inorganic, the polymer is coated on the outer surface of the de-icing salt; When the de-icing salt is an organic de-icing salt, the de-icing salt is linked to the polymer. The plant-based cellulose content is 5-30 wt% of the acrylic acid mass; the content of the organically modified clay mineral inorganic components is 2-10 wt% of the acrylic acid mass; the amount of ice-melting salt is 150-400 wt% of the acrylic acid mass; and the amount of acrylamide derivative is 20-40 wt% of the acrylic acid mass.

2. The plant-based recyclable road de-icing agent according to claim 1, characterized in that: The plant-based cellulose is bagasse cellulose, coconut shell cellulose, peanut shell cellulose, or rice straw cellulose. The organically modified clay mineral inorganic components are attapulgite, halloysite, bentonite, kaolin, or laterite. The acrylamide derivative is acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N-isopropylacrylamide, or N-hydroxyethylacrylamide; The inorganic de-icing salt is calcium chloride, sodium chloride, or magnesium chloride; The organic de-icing salt is potassium acetate or sodium acetate.

3. A method for preparing a plant-based recyclable road de-icing agent, characterized in that, Includes the following steps: Step S1: Prepare plant-based cellulose; Step S2: Preparation of organically modified clay mineral inorganic components: The inorganic components of clay minerals are dissolved in an organic solvent, and then a modifier is added to obtain a mixture. The mixture is heated to 60-80℃, and the pH value of the mixture is adjusted to 8-10 with NaOH solution. The mixture is stirred continuously for 3-5 hours, cooled, filtered to remove impurities, washed, filtered by suction, dried at 50-80℃ to constant weight, pulverized, and sieved to obtain the organically modified inorganic components of clay minerals. Step S3: Preparation of plant-based recyclable road de-icing agent: S3.1 Preparation of mixed solution B: After neutralizing acrylic acid, acrylic acid, acrylamide derivative and ice-melting salt are mixed under the action of crosslinking agent and initiator to form mixed solution B; S3.2 Dissolve the organically modified clay mineral inorganic components and plant-based cellulose in water, introduce inert gas, heat to 50-80℃ and stir continuously for 30-60 minutes to obtain a uniformly mixed emulsion. S3.

3. Slowly add mixed solution B to the emulsion and react for 2-4 hours to obtain crude product; dry the crude product at 50-80℃ to constant weight, crush and sieve to obtain plant-based recyclable road de-icing agent.

4. The preparation method of the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, Step S1 specifically includes the following steps: S1.1 Powdering: Boil the plant-based raw material for 30-60 minutes, dry it, then mechanically crush and grind it into powder; S1.2 Alkaline hydrolysis: Weigh the powder and pour it into an alkaline solution of NaOH and H2O2. React at 80-100℃ for 2-4 hours with stirring. Cool and filter, wash with water until neutral, filter again, and then dry at 50-70℃ to constant weight to obtain alkaline hydrolysis product A1. S1.3 Acid hydrolysis: Weigh the product A1 after alkaline hydrolysis and pour it into H2SO4 solution. Heat to 80-100℃ and stir continuously for 3-5 hours. Filter out impurities, and dry by vacuum filtration to obtain acid hydrolysis product A2. S1.4 Bleaching: Weigh the acid hydrolysis product A2 and pour it into a sodium chlorite solution. Adjust the pH of the solution to 4-6 with glacial acetic acid. Stir the reaction at 70-90℃ for 3-6 hours. Wash with water until the pH is neutral. After drying, white plant-based cellulose is obtained.

5. The preparation method of the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, In step S1, the plant base is bagasse, coconut shell, peanut shell or rice straw; the clay mineral inorganic component is attapulgite, halloysite, bentonite, kaolin or red clay.

6. The method for preparing the plant-based recyclable road de-icing agent as described in claim 4, characterized in that, In step S1, the mass fraction of NaOH in the mixed solution of NaOH and H2O2 during the alkaline hydrolysis process is 3-10 wt%, the mass fraction of H2O2 is 0.5-1 wt%, and the solid-liquid ratio is 1:10-1:

20. During the acidolysis process, the volume fraction of H2SO4 is 1-3% v / v, and the solid-liquid ratio is 1:10-1:20; during the bleaching process, the volume fraction of sodium chlorite is 1-5 wt%, and the solid-liquid ratio is 1:10-1:

20.

7. The method for preparing the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, In step S2, the modifier is KH-550, KH-560, KH-570, KH-590, KH-602 or KH-792, and the solid-liquid ratio of the inorganic component to the modifier is 1:0.8-1:1.

5.

8. The method for preparing the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, In step S3, the content of plant-based cellulose is 5-30 wt% of the acrylic acid content. The content of inorganic components in organically modified clay minerals is 2-10 wt% of the acrylic acid content; The amount of acrylamide derivative used is 20-40 wt% of the amount of acrylic acid used; The amount of crosslinking agent used is 0.10-0.25 wt% of the amount of acrylic acid; The amount of initiator used is 0.4-0.12 wt% of the amount of acrylic acid; The amount of de-icing salt used is 150-400 wt% of the amount of acrylic acid used.

9. The method for preparing the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, In step 3, acrylic acid is neutralized with NaOH to a degree of neutralization of 50-80%.

10. The method for preparing the plant-based recyclable road de-icing agent as described in claim 3, characterized in that, In step S3, the acrylamide derivative is acrylamide, 2-acrylamido-2-methyl-1-propanesulfonic acid, N-isopropylacrylamide, or N-hydroxyethylacrylamide; The crosslinking agent is N,N'-methylenebisacrylamide; The initiator is ammonium persulfate or potassium persulfate; The de-icing salt is calcium chloride, sodium chloride, magnesium chloride, potassium acetate, or sodium acetate.

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