Non-chlorine snowmelt agent, method for preparing same, and use thereof

Abstract

This invention belongs to the field of de-icing agent technology, specifically relating to a non-chlorine de-icing agent, its preparation method, and its application. The non-chlorine de-icing agent comprises the following raw materials in parts by weight: 60-80 parts antifreeze, 10-20 parts exothermic agent, and 5-10 parts modified starch-sodium polyacrylate composite. The non-chlorine de-icing agent provided by this invention, containing a modified starch-sodium polyacrylate composite as a raw material, has a composite hydrophilic layer. This layer enhances the adsorption capacity of the modified starch-sodium polyacrylate composite for antifreeze, preventing the antifreeze from crystallizing and agglomerating on the particle surface; it also reduces the direct contact of the antifreeze with metal products and asphalt, protecting the road structure. Furthermore, the modified starch-sodium polyacrylate composite exhibits good biodegradability and strong environmental friendliness.

Description

Technical Field

[0001] This invention belongs to the field of de-icing agent technology, specifically relating to a non-chlorine de-icing agent, its preparation method, and its application. Background Technology

[0002] Chloride ions in chloride-based de-icing agents are highly corrosive, severely corroding metal products such as vehicles and underground pipelines. Furthermore, chlorides are difficult to degrade in the environment, accumulating over time and causing persistent damage. To address this, existing technologies have proposed non-chlorine-based de-icing agents, typically organic de-icing agents such as metal acetates. To reduce the corrosiveness of these agents, various corrosion inhibitors (such as phosphates, molybdates, and organic amines) are added. However, these inhibitors have limited specificity, poor stability in low temperatures or complex water conditions, and their corrosiveness remains relatively severe. Moreover, even with organic de-icing agents like potassium acetate, their aqueous solutions can still accelerate the stripping and aging of asphalt pavements through penetration and freeze-thaw cycles, causing physicochemical erosion of the road surface. Summary of the Invention

[0003] To address the aforementioned problems, this invention provides a non-chlorine-based de-icing agent, its preparation method, and its application, thereby resolving at least one aspect of the technical issues described above.

[0004] This invention is achieved through the following technical solution: In a first aspect, the present invention provides a non-chlorine de-icing agent, comprising the following raw materials in parts by weight: 60-80 parts antifreeze, 10-20 parts effervescent agent, and 5-10 parts modified starch-sodium polyacrylate composite.

[0005] Secondly, the present invention provides a method for preparing the above-mentioned non-chlorine de-icing agent, comprising the following steps: The antifreeze, effervescent agent, and modified starch-sodium polyacrylate complex are mixed and granulated according to a preset ratio.

[0006] Thirdly, the present invention provides an application of the above-mentioned non-chlorine de-icing agent in snow or ice surfaces.

[0007] The non-chlorine de-icing agent provided by this invention has at least the following beneficial technical effects compared with the prior art: The non-chlorine de-icing agent provided by this invention comprises a modified starch-sodium polyacrylate composite as its raw material. This composite hydrophilic layer enhances the adsorption capacity of the modified starch-sodium polyacrylate composite for antifreeze, preventing antifreeze from crystallizing and agglomerating on the particle surface. It also reduces direct contact between the antifreeze and metal products and asphalt, protecting the road structure. Furthermore, the modified starch-sodium polyacrylate composite exhibits good biodegradability and is highly environmentally friendly.

[0008] The method for preparing the non-chlorine de-icing agent provided by this invention has at least the following beneficial technical effects compared with the prior art: The method for preparing non-chlorine de-icing agent provided by the present invention involves mixing and treating the modified starch-sodium polyacrylate composite to fully adsorb the antifreeze and the exothermic agent, forming wet granules with high moisture content, thus preventing the granules from absorbing moisture and clumping during granulation. Detailed Implementation

[0009] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described and illustrated below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention. All other embodiments obtained by those skilled in the art based on the embodiments provided by this invention without inventive effort are within the scope of protection of this invention.

[0010] Obviously, the following description is merely some examples or embodiments of the present invention. Those skilled in the art can apply the present invention to other similar scenarios without any inventive effort. Furthermore, it is understood that although the effort involved in such development may be complex and lengthy, for those skilled in the art related to the content disclosed in this invention, modifications to design, manufacturing, or production based on the technical content disclosed in this invention are merely conventional technical means and should not be construed as insufficient disclosure of the present invention.

[0011] However, there may be instances where unnecessary detailed descriptions are omitted. For example, detailed descriptions of well-known matters or repetitive descriptions of essentially the same structures may be omitted. This is to avoid making the following description unnecessarily lengthy and to facilitate understanding by those skilled in the art. Furthermore, the following description is provided to enable those skilled in the art to fully understand the invention and is not intended to limit the subject matter of the claims.

[0012] Unless otherwise specified, all embodiments and optional embodiments of the present invention can be combined with each other to form new technical solutions, and all technical features and optional technical features of the present invention can be combined with each other to form new technical solutions.

[0013] Non-chlorine de-icing agents The first aspect of this invention provides a non-chlorine de-icing agent, comprising the following raw materials in parts by weight: 60-80 parts antifreeze, 10-20 parts effervescent agent, and 5-10 parts modified starch-sodium polyacrylate composite.

[0014] The non-chlorine de-icing agent provided in this invention comprises a modified starch-sodium polyacrylate composite as its raw material. This composite hydrophilic layer enhances the adsorption capacity of the modified starch-sodium polyacrylate composite for antifreeze, preventing the antifreeze from crystallizing and agglomerating on the particle surface. It also reduces the direct contact of the antifreeze with metal products and asphalt, protecting the road structure. Furthermore, the modified starch-sodium polyacrylate composite exhibits good biodegradability and strong environmental friendliness.

[0015] In some embodiments, the antifreeze agent includes at least one of potassium acetate and sodium acetate. In this case, the strong electrolyte properties of potassium acetate and sodium acetate significantly lower the freezing point of non-chlorine de-icing agents, and they also exhibit good biodegradability and are environmentally friendly.

[0016] In some embodiments, the heating agent includes at least one of ethylene glycol and propylene glycol. In this case, ethylene glycol and propylene glycol have exothermic dissolving properties, which can rapidly provide heat at low temperatures, disrupt the ice crystal structure, and accelerate melting.

[0017] In some embodiments, the modified starch-sodium polyacrylate composite comprises the following raw materials in parts by weight: 20 parts modified starch, 77-80 parts acrylic acid, 0.92-1 part ammonium persulfate (APS) and 0.062-0.07 parts N,N'-methylenebisacrylamide (MBA).

[0018] In the preparation of the modified starch-sodium polyacrylate composite, the modified starch serves as the amphiphilic backbone core. Its hydrophobic long chains can undergo hydrophobic association during subsequent polymerization, forming physical crosslinking points. This, in conjunction with the chemical crosslinking network, constructs a composite hydrophilic layer that combines rigidity and flexibility. Acrylic acid provides hydrophilic segments with high ionic strength. Ammonium persulfate (APS) acts as an initiator, triggering the polymerization of acrylic acid. N,N'-methylenebisacrylamide (MBA), as a crosslinking agent, provides chemical crosslinking points, which, in conjunction with the physical hydrophobic crosslinking points of the modified starch, form a stable three-dimensional network.

[0019] In some embodiments, the modified starch comprises the following raw materials in parts by weight: 100 parts starch, 3 to 5 parts octenyl succinic anhydride (OSA) and 3 to 5 parts base catalyst.

[0020] In the above-mentioned raw materials for preparing modified starch, starch serves as the main reactant, providing hydroxyl groups on glucose units as reaction sites; octenyl succinic anhydride serves as a modifier, reacting with starch hydroxyl groups to introduce octenyl succinic acid groups containing both hydrophobic long chains (octenyl) and hydrophilic carboxyl groups, thus endowing starch with amphiphilicity; an alkaline catalyst maintains the reaction system in a weakly alkaline environment, which is the optimal pH condition for the nucleophilic substitution reaction between octenyl succinic anhydride (OSA) and starch hydroxyl groups.

[0021] In some embodiments, starch includes corn starch.

[0022] In some embodiments, the moisture content of the starch is less than 14%.

[0023] In some embodiments, the alkaline catalyst includes at least one of sodium hydroxide solution and potassium hydroxide solution.

[0024] In some embodiments, the concentration of the sodium hydroxide solution is 0.03 g / ml to 0.05 g / ml.

[0025] In some embodiments, the concentration of the potassium hydroxide solution is 0.03 g / ml to 0.05 g / ml.

[0026] Preparation method of non-chlorine de-icing agent A second aspect of this invention provides a method for preparing a non-chlorine-based de-icing agent, comprising the following steps: S10. The antifreeze, exothermic agent and modified starch-sodium polyacrylate complex are mixed and granulated according to the preset ratio.

[0027] The method for preparing non-chlorine de-icing agent provided in this invention involves mixing the modified starch-sodium polyacrylate composite to fully adsorb the antifreeze and heating agent, forming wet granules with high moisture content, thus preventing the granules from absorbing moisture and clumping during granulation.

[0028] In some embodiments, the preparation of the modified starch-sodium polyacrylate composite in step S10 above includes the following steps: S101. After neutralizing the acrylic acid, it is mixed with the modified starch slurry to obtain a mixture.

[0029] S102. After the mixture and ammonium persulfate are mixed and initiated, they are crosslinked with N,N'-methylenebisacrylamide.

[0030] In the preparation of the modified starch-sodium polyacrylate composite, the neutralization treatment causes the acrylic acid to partially generate acrylate, controlling the degree of monomer ionization and thus controlling the reactivity, water absorption, and gel strength during subsequent acrylic acid polymerization. The mixed initiation treatment causes the acrylic acid monomer to polymerize at the starch free radical sites, forming a starch-g-sodium polyacrylate covalent structure. The crosslinking treatment causes N,N'-methylenebisacrylamide to form a chemical crosslinking network (hydrophilic) between the polyacrylate chains. At the same time, the octenyl long chains on the modified starch chains strongly associate under the drive of polymerization heat and hydrophobic effect to form physically crosslinked microdomains (hydrophobic). The two interpenetrate and cooperate to form a composite hydrophilic layer structure.

[0031] In some embodiments, after neutralizing the acrylic acid in step S101 above, the degree of neutralization is 65% to 75%.

[0032] In some embodiments, the preparation of the modified starch slurry in step S101 above includes the following steps: S1011. After mixing modified starch and water, gelatinize the mixture and cool it to 35℃~40℃ to obtain modified starch slurry.

[0033] In the preparation of the modified starch slurry, gelatinization is used to break down starch particles, allowing the hydrophobic octenyl molecular chains in the modified starch to fully extend; during the cooling process to 35℃~40℃, the hydrophobic segments begin to pre-aggregate, forming a weak physical cross-linking network prototype.

[0034] In some embodiments, in step S1011 above, the mass-volume ratio of modified starch to water is (4g~8g):100ml.

[0035] In some embodiments, in step S1011 above, the temperature of the gelatinization process is 85°C to 90°C.

[0036] In some embodiments, the gelatinization process in step S1011 is performed for 35 min to 45 min.

[0037] In some embodiments, the preparation of modified starch in step S1011 above includes the following steps: S10111. Starch milk is subjected to alkali treatment with an alkaline catalyst to obtain alkali-treated starch milk.

[0038] S10112. Alkaline starch milk and octenyl succinic anhydride are subjected to esterification treatment, and then the treatment is terminated. The mixture is then purified and dried to obtain modified starch.

[0039] In the preparation of the modified starch described above, the alkalization treatment partially deprotonates the starch hydroxyl groups, forming more nucleophilic starch oxygen anions and creating the necessary alkaline environment for the subsequent esterification reaction; the esterification treatment introduces octenyl succinic anhydride groups into the starch, resulting in modified starch containing octenyl succinic anhydride groups; the termination treatment terminates the esterification reaction, ensuring that the carboxylic acid on the grafted octenyl succinic anhydride groups remains -COOH or -COO. - The form affects the charge characteristics of the final product.

[0040] In some embodiments, in step S10111 above, the mass-volume ratio of starch to water in the starch milk is 100g:(150ml~170ml).

[0041] In some embodiments, in step S10111 above, the alkalization treatment includes the following steps: While stirring, an alkaline catalyst is added dropwise to the starch slurry.

[0042] In some embodiments, in step S10111 above, the pH value of the alkalized starch milk is 8 to 8.5.

[0043] In some embodiments, in step S10111 above, the stirring speed is 100 rpm to 200 rpm.

[0044] In some embodiments, in step S10112 above, the esterification treatment includes the following steps: s1. While stirring, maintain the pH of the reaction system at 8.0~8.5, add octenyl succinic anhydride dropwise into the alkalized starch milk, and continue stirring the reaction after the addition is complete.

[0045] In some embodiments, in step s1 above, the stirring speed is 700 rpm to 900 rpm.

[0046] In some embodiments, in step s1 above, sodium hydroxide solution is used to maintain the pH of the reaction system at 8.0 to 8.5.

[0047] In some embodiments, in step s1 above, the time for adding octenyl succinic anhydride to the alkalized starch milk is 20 min to 30 min.

[0048] In some embodiments, in step s1 above, the stirring reaction continues for 4 to 6 hours.

[0049] In some embodiments, in step S10112 above, the termination process includes the following steps: s2. Adjust the pH of the reaction system to neutral.

[0050] In some embodiments, in step s2 above, the pH of the reaction system is adjusted to neutral using a dilute HCl solution.

[0051] In some embodiments, in step S10112 above, purification includes the following steps: s3. Obtain the solids from the reaction mixture obtained from the termination treatment, wash the solids with water, and then wash with an ethanol-water solution.

[0052] In the above purification process, water washing removes the salts from the solid, and the ethanol aqueous solution can efficiently dissolve and wash away unreacted OSA, its hydrolysis products, and low-substituted byproducts, thereby obtaining pure modified starch while retaining its amphiphilic structure.

[0053] In some embodiments, in step s3 above, the solids in the reaction mixture obtained from the termination process are obtained by filtration or centrifugation.

[0054] In some embodiments, the number of times the water is washed in step s3 above is 2 to 3.

[0055] In some embodiments, in step s3 above, the volume fraction of ethanol in the aqueous ethanol solution is 70% to 75%.

[0056] In some embodiments, in step s3 above, the washing with ethanol aqueous solution is performed 2 to 3 times.

[0057] In some embodiments, the drying step in step S10112 above includes: s4. Dry the purified solid at 40℃~45℃ to constant weight (moisture content ≤10%).

[0058] In the above drying steps, low-temperature drying can avoid the thermal degradation of long-chain octenyl succinic anhydride or starch gelatinization.

[0059] In some embodiments, in step S1011 above, the degree of substitution of the modified starch is 0.015 to 0.02.

[0060] In some embodiments, the mixed initiation process in step S102 above includes: S1021. Under a nitrogen atmosphere, the mixture is heated to 60℃~65℃ and then ammonium persulfate is added for initiation.

[0061] In the above steps of mixing the mixture with ammonium persulfate, a nitrogen atmosphere can eliminate oxygen to inhibit polymerization; at 60℃~65℃, ammonium persulfate decomposes to generate free radicals, which attack the active hydrogen on the modified starch chain to form macromolecular free radicals; which in turn initiate the polymerization of acrylic acid monomers at the starch free radical sites to form a starch-g-sodium polyacrylate covalent structure.

[0062] In some embodiments, the triggering time in step S1021 is 15 min to 20 min.

[0063] In some embodiments, in step S102 above, the crosslinking treatment includes the following steps: S1022. At a constant temperature, N,N'-methylenebisacrylamide is added to the mixed system after the initiation treatment to carry out a crosslinking reaction.

[0064] In some embodiments, in step S1022 above, the constant temperature is 61℃±1℃.

[0065] In some embodiments, in step S1022 above, the crosslinking reaction time is 3h to 4h.

[0066] In some embodiments, the preparation of the modified starch-sodium polyacrylate composite in step S10 above further includes the following steps: S103. Curing and post-treatment.

[0067] In some embodiments, in step S103 above, ripening includes the following steps: S1031. The product obtained by cross-linking treatment is kept at a certain temperature and then allowed to stand to obtain a gel.

[0068] In the above-mentioned ripening process, ripening ensures complete reaction and network stability.

[0069] In some embodiments, in step S1031 above, the temperature for heat preservation is 61℃±1℃.

[0070] In some embodiments, in step S1031 above, the heat preservation time is 1h to 1.5h.

[0071] In some embodiments, in step S1031 above, the settling time is 24h~25h.

[0072] In some embodiments, in step S103 above, the post-processing includes the following steps: S1032. After washing the gel material by soaking it in an ethanol aqueous solution, dry it to a constant weight.

[0073] In the above post-processing steps, soaking and washing with ethanol aqueous solution purifies the gel material and enhances the hydrophobic association, so that the "composite hydrophilic layer" structure can be "fixed" in the dry state and can be quickly reconstructed when in use (when exposed to water).

[0074] In some embodiments, in step S1032 above, the ethanol aqueous solution is used for soaking and washing 3 to 4 times.

[0075] In some embodiments, in step S1032 above, the drying temperature is 70°C to 80°C.

[0076] In some embodiments, the mixing process in step S10 above includes the following steps: S104. After mixing the antifreeze and the exothermic agent with stirring, mix them with the modified starch-sodium polyacrylate complex.

[0077] In some embodiments, in step S104 above, the temperature at which the antifreeze and the exothermic agent are mixed is below 0°C.

[0078] In some embodiments, granulation in step S10 above includes the following steps: S105. The product obtained from the mixed treatment is granulated by spray drying or rotary granulation process.

[0079] In some embodiments, the drying temperature in step S105 is 80°C to 100°C. This ensures that the structure of the product obtained from the mixing process is not damaged by high temperatures, while reducing residual moisture and improving storage stability.

[0080] In some embodiments, in step S105 above, the average particle size is 6 mm to 8 mm.

[0081] The following detailed description is provided with reference to specific embodiments. For ease of explanation, in the comparative examples below, where the stirring speed is not limited, all are conventional stirring methods in the art and are not particularly limited in the embodiments of the present invention.

[0082] Example 1 Example 1 provides a non-chlorine de-icing agent, composed of the following raw materials in parts by weight: 40 parts potassium acetate, 40 parts sodium acetate, 10 parts ethylene glycol, 10 parts propylene glycol, 8 parts modified starch-sodium polyacrylate composite; The modified starch-sodium polyacrylate composite is composed of the following raw materials in parts by weight: 20 parts modified starch, 77 parts acrylic acid, 0.92 parts ammonium persulfate (APS) and 0.062 parts N,N'-methylenebisacrylamide.

[0083] The modified starch is composed of the following raw materials in parts by weight: 100 parts corn starch, 4 parts octenyl succinic anhydride (OSA) and 4 parts sodium hydroxide solution (0.03 g / ml).

[0084] This embodiment also provides a method for preparing the above-mentioned non-chlorine de-icing agent, the steps of which are as follows: E10. Preparation of Modified Starch E101. Alkalization treatment: While stirring at 100 rpm, add sodium hydroxide solution (0.03 g / ml) dropwise to the starch slurry until the pH value is 8.5 to obtain alkalized starch slurry; In the starch milk, the mass-volume ratio of starch to water is 100g:150ml.

[0085] E102. Esterification treatment: Under stirring at 800 rpm, the pH of the reaction system was maintained at 8.5 using sodium hydroxide solution (0.03 g / ml). Octenyl succinic anhydride was added dropwise to the alkalized starch milk. After the addition was completed in 20 min, the reaction was stirred for another 4 h.

[0086] E103. Termination treatment: Adjust the pH of the reaction system to neutral using dilute HCl solution.

[0087] E104. Purification: Centrifuge to obtain the solids in the reaction mixture obtained from the termination treatment, wash the solids three times with water, and then wash them three times with an ethanol-water solution. In the aqueous ethanol solution, the volume fraction of ethanol is 70%.

[0088] E105. Drying: The washed solids are dried at 40°C to constant weight to obtain modified starch.

[0089] E20. Preparation of modified starch-sodium polyacrylate composite E201. Preparation of modified starch slurry: Modified starch and water are mixed, gelatinized, and then cooled to 40°C to obtain modified starch slurry; The modified starch and water had a mass-to-volume ratio of 6g:100ml; the gelatinization treatment was carried out at a temperature of 85℃ for 45 minutes.

[0090] E202. Preparation of the mixture: After neutralizing the acrylic acid to a degree of neutralization of 70%, it is mixed with the modified starch slurry to obtain the mixture.

[0091] E203. Mixed Initiation Treatment: Under a nitrogen atmosphere, the mixture is heated to 60°C and then ammonium persulfate is added for initiation to obtain a mixed system after mixed initiation treatment; The initiation time is 15 minutes.

[0092] E204. Crosslinking treatment: At a constant temperature, N,N'-methylenebisacrylamide was added to the mixed system after the initiation treatment and the crosslinking reaction was carried out for 3 hours.

[0093] E205. Curing: The product obtained by cross-linking treatment is kept at 61℃±1℃ for 1 hour and then allowed to stand for 24 hours to obtain a gel.

[0094] E206. Post-treatment: The gel material was soaked and washed three times with an ethanol aqueous solution (ethanol volume fraction of 70%), dried at 75°C to constant weight, and then pulverized through a 100-mesh sieve to obtain the modified starch-sodium polyacrylate composite.

[0095] E30. Preparation of non-chlorine de-icing agents E301. Mixing treatment: Mix the antifreeze and the exothermic agent at 0°C with stirring according to the preset ratio, and then mix with the modified starch-sodium polyacrylate composite.

[0096] E302. Granulation: The product obtained from the mixing process is made into granules with an average particle size of 7mm using a spray drying process, which is the non-chlorine de-icing agent in this embodiment; The drying temperature is 80℃.

[0097] Example 2 Example 2 provides a non-chlorine de-icing agent, composed of the following raw materials in parts by weight: 30 parts potassium acetate, 30 parts sodium acetate, 5 parts ethylene glycol, 5 parts propylene glycol, 5 parts modified starch-sodium polyacrylate composite. The modified starch-sodium polyacrylate composite is composed of the following raw materials in parts by weight: 20 parts modified starch, 77 parts acrylic acid, 0.92 parts ammonium persulfate (APS) and 0.062 parts N,N'-methylenebisacrylamide.

[0098] The modified starch is composed of the following raw materials in parts by weight: 100 parts corn starch, 3 parts octenyl succinic anhydride (OSA) and 3 parts sodium hydroxide solution (0.03 g / ml).

[0099] This embodiment also provides a method for preparing the above-mentioned non-chlorine de-icing agent, the steps of which are basically the same as those in Example 1.

[0100] Example 3 Example 3 provides a non-chlorine de-icing agent, composed of the following raw materials in parts by weight: 40 parts potassium acetate, 40 parts sodium acetate, 10 parts ethylene glycol, 10 parts propylene glycol, 10 parts modified starch-sodium polyacrylate composite. The modified starch-sodium polyacrylate composite is composed of the following raw materials in parts by weight: 20 parts modified starch, 77 parts acrylic acid, 0.92 parts ammonium persulfate (APS) and 0.062 parts N,N'-methylenebisacrylamide.

[0101] The modified starch is composed of the following raw materials in parts by weight: 100 parts corn starch, 5 parts octenyl succinic anhydride (OSA) and 5 parts sodium hydroxide solution (0.03 g / ml).

[0102] This embodiment also provides a method for preparing the above-mentioned non-chlorine de-icing agent, the steps of which are basically the same as those in Example 1.

[0103] Comparative Example 1 Comparative Example 1 provides a non-chlorine de-icing agent, composed of the following raw materials in parts by weight: 40 parts potassium acetate, 40 parts sodium acetate, 10 parts ethylene glycol, 10 parts propylene glycol, 4 parts starch and 4 parts sodium polyacrylate.

[0104] This comparative example also provides a method for preparing a non-chlorine de-icing agent, the steps of which are as follows: D10. According to the preset ratio, the antifreeze and the exothermic agent are mixed at 0°C under stirring, and then starch and sodium polyacrylate are added to obtain a mixture.

[0105] D20. The mixture is prepared into particles with an average particle size of 7 mm by spray drying process, which is the non-chlorine de-icing agent of this comparative example; The drying temperature is 80℃.

[0106] To verify the advancement of the non-chlorine de-icing agent and its preparation method provided in the embodiments of the present invention, the non-chlorine de-icing agents prepared in the embodiments and comparative examples of the present invention were tested according to standard GB / T23851 for solid dissolution rate (g / min), carbon steel corrosion rate (mm / a) and road surface friction attenuation rate (%). The results are shown in Table 1 below.

[0107] Table 1

[0108] From Table 1 above, at least the following conclusions can be drawn: In Comparative Example 1, without the modified starch-sodium polyacrylate composite, the corrosion rate of carbon steel increased significantly. Although the solid dissolution rate and pavement friction attenuation rate met the standard GB / T23851, they were both close to the critical values ​​and not ideal. This demonstrates that the inclusion of the modified starch-sodium polyacrylate composite in the raw materials provides a composite hydrophilic layer, which can enhance the adsorption capacity of the modified starch-sodium polyacrylate composite for antifreeze, preventing antifreeze from crystallizing and agglomerating on the particle surface; it can also reduce the direct contact of the antifreeze with metal products and asphalt, protecting the road structure. Furthermore, the modified starch-sodium polyacrylate composite exhibits good biodegradability and strong environmental friendliness.

[0109] It should be noted that the present invention is not limited to the above-described embodiments. The above embodiments are merely examples, and any embodiments that have the same structure and perform the same effects as the technical concept within the scope of the present invention are included within the scope of the present invention. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments, and other ways of constructing by combining some of the constituent elements of the embodiments, without departing from the spirit of the present invention, are also included within the scope of the present invention.

Claims

1. A non-chlorine de-icing agent, characterized in that, The preparation materials include the following parts by weight: 60-80 parts antifreeze, 10-20 parts effervescent agent, and 5-10 parts modified starch-sodium polyacrylate composite.

2. The non-chlorine de-icing agent according to claim 1, characterized in that, It satisfies at least one of the following characteristics (1) to (4): (1) The antifreeze agent includes at least one of potassium acetate and sodium acetate; (2) The heating agent includes at least one of ethylene glycol and propylene glycol; (3) The modified starch-sodium polyacrylate composite comprises the following raw materials in parts by weight: 20 parts modified starch, 77-80 parts acrylic acid, 0.92-1 part ammonium persulfate and 0.062-0.07 parts N,N'-methylenebisacrylamide; (4) The modified starch comprises the following raw materials in parts by weight: 100 parts starch, 3 to 5 parts octenyl succinic anhydride and 3 to 5 parts alkaline catalyst.

3. The non-chlorine de-icing agent according to claim 2, characterized in that, The modified starch satisfies at least one of the following characteristics (1) to (3): (1) Starch includes corn starch; (1) The moisture content of the starch is below 14%; (3) The alkaline catalyst includes at least one of sodium hydroxide solution and potassium hydroxide solution.

4. A method for preparing a non-chlorine-based de-icing agent as described in any one of claims 1 to 3, characterized in that, Includes the following steps: The antifreeze, effervescent agent, and modified starch-sodium polyacrylate complex are mixed and granulated according to a preset ratio.

5. The method for preparing the non-chlorine de-icing agent according to claim 4, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) The preparation of the modified starch-sodium polyacrylate composite includes the following steps: After neutralizing the acrylic acid, it is mixed with the modified starch slurry to obtain a mixture. After the mixture and ammonium persulfate are mixed and initiated, they are crosslinked with N,N'-methylenebisacrylamide. (2) The mixing process includes the following steps: The antifreeze and the exothermic agent were mixed with a stirring mixture and then mixed with a modified starch-sodium polyacrylate complex. (3) The granulation process includes the following steps: The product obtained from the mixed treatment is granulated using spray drying or rotary granulation processes.

6. The method for preparing the non-chlorine de-icing agent according to claim 5, characterized in that, It satisfies at least one of the following characteristics (1) to (3): (1) In the preparation of the modified starch-sodium polyacrylate composite, at least one of the following characteristics 1) to 4) is satisfied: 1) The preparation of modified starch slurry includes the following steps: Modified starch and water are mixed, gelatinized, and then cooled to 35℃~40℃ to obtain modified starch slurry; 2) The steps of the mixed initiation treatment include: Under a nitrogen atmosphere, the mixture is heated to 60℃~65℃ and then ammonium persulfate is added for initiation; 3) The crosslinking treatment includes the following steps: At a constant temperature, N,N'-methylenebisacrylamide was added to the mixed system after initiation treatment to carry out a crosslinking reaction; 4) The preparation of the modified starch-sodium polyacrylate composite also includes the following steps: Aging and post-processing; (2) In the mixing process, the temperature at which the antifreeze and the exothermic agent are mixed is below 0°C; (3) In the granulation process, at least one of the following characteristics 1) to 2) is satisfied: 1) The drying temperature is 80℃~100℃; 2) The average particle size is 6mm~8mm.

7. The method for preparing the non-chlorine de-icing agent according to claim 6, characterized in that, It satisfies at least one of the following characteristics (1) to (4): (1) In the preparation of the modified starch slurry, at least one of the following characteristics 1) to 3) is satisfied: 1) The mass-to-volume ratio of modified starch to water is 4g~8g:100ml; 2) The gelatinization temperature is 85℃~90℃; 3) The gelatinization process should be completed in 35-45 minutes. (2) In the mixed initiation process, the initiation time is 15 min to 20 min; (3) In the crosslinking treatment, at least one of the following characteristics 1) to 2) is satisfied: 1) The constant temperature is 61℃±1℃; 2) The cross-linking reaction takes 3-4 hours; (4) In the preparation of the modified starch-sodium polyacrylate composite, at least one of the following characteristics 1) to 2) is satisfied: 1) The maturation process includes the following steps: The product obtained by cross-linking treatment was kept at a certain temperature and then allowed to stand to obtain a gel. 2) Post-processing includes the following steps: The gel material was washed by soaking in an aqueous ethanol solution and then dried to a constant weight.

8. The application of a non-chlorine de-icing agent as described in any one of claims 1 to 3 on snow or ice surfaces.

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