Special corrosion inhibitor for composite snow-melting agent and preparation method thereof
By using a composite corrosion inhibitor of modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose, and polyamide amine (PAMAM), the problems of low effective concentration, poor film formation, and poor stability of existing corrosion inhibitors for de-icing agents have been solved, achieving a highly efficient corrosion inhibition effect under low temperature and pH fluctuation environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-01-05
- Publication Date
- 2026-03-27
AI Technical Summary
Existing corrosion inhibitors for de-icing agents have too low effective concentrations, poor film-forming properties, and poor stability. They are particularly ineffective in environments with low temperatures and large pH fluctuations, and their corrosion inhibition efficiency for non-chlorine de-icing agents is not high.
A composite corrosion inhibitor with modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose and polyamide amine (PAMAM) as the main components is prepared by combining nonionic surfactants and synergists through a specific reaction to improve the adsorption capacity and stability of the composite de-icing agent.
It achieves stable protection of metal products in an environment of -20℃, significantly reduces corrosion, has wide applicability, and can maintain corrosion inhibition effect in environments with large pH fluctuations.
Smart Images
Figure SMS_1 
Figure SMS_2 
Figure SMS_3
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to a composite snow-melting agent special corrosion inhibitor and a preparation method thereof. BACKGROUND
[0002] Traditional snow-melting agents (such as sodium chloride, calcium chloride, etc.) and non-chlorine type snow-melting agents are widely used in winter road snow removal, but they have strong corrosiveness to metal facilities (such as bridges, vehicles) and concrete structures, resulting in economic losses and environmental problems. Currently, commercially available corrosion inhibitors have problems such as high cost, low corrosion inhibition efficiency or environmental pollution. Therefore, it is of great significance to develop a high-efficiency, environmentally friendly and economical snow-melting agent special corrosion inhibitor.
[0003] The applicant found in the research that the existing snow-melting agent special corrosion inhibitor has the following problems: First, the existing snow-melting agent special corrosion inhibitor has low effective concentration, poor film-forming property and unsatisfactory corrosion inhibition effect, and often needs to reach a high concentration to have corrosion inhibition effect, which is too high in use cost.
[0004] Second, the existing snow-melting agent special corrosion inhibitor has poor stability and unsatisfactory corrosion inhibition effect in an environment with low temperature and large pH fluctuation. Currently, snow-melting agents are required to be used under the condition of-10℃ to-20℃, and under this low temperature, the corrosion inhibition performance of the existing snow-melting agent special corrosion inhibitor is not ideal, and the effect is unstable in actual operation with large temperature fluctuation.
[0005] Third, the existing snow-melting agent special corrosion inhibitor has low corrosion inhibition efficiency for non-chlorine type snow-melting agents. At present, some important infrastructure facilities such as airports and highways use a large amount of non-chlorine type corrosion inhibitors, and a composite corrosion inhibitor is needed to improve the corrosion inhibition effect and reduce the corrosion of important facilities.
[0006] At present, there is an urgent need for a composite snow-melting agent special corrosion inhibitor that can effectively protect infrastructure and has good stability, and therefore the present application provides a snow-melting agent special corrosion inhibitor with high film-forming property, good hydrophilicity, strong corrosion inhibition effect and long-term effect. SUMMARY
[0007] The technical problem to be solved by the present application is to provide a composite snow-melting agent special corrosion inhibitor and a preparation method thereof, which can significantly reduce the corrosion of snow-melting agents.
[0008] To achieve one of the above-mentioned purposes, the composite snow-melting agent special corrosion inhibitor provided by the present application includes the following components in a mass percentage ratio: The modified passivator is 15%-20%, the dispersant is 10%-15%, the non-ionic surfactant is 5%-10%, the synergist is 10%-12%, and the rest is deionized water.
[0009] The passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose, and polyamide amine (PAMAM).
[0010] The mass ratio of the modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose, and polyamide amine is 2:2-3:1-2.
[0011] The modified 1-hydroxyethylidene-1,1-diphosphoric acid is prepared by the following steps: 1-Hydroxyethylidene-1,1-diphosphoric acid (HEDP) was mixed with ethanol, and sodium hydrosulfide (NaHS) was slowly added under nitrogen protection, stirring, and at 25°C. After the addition of sodium hydrosulfide (NaHS) was complete, the reaction was carried out under nitrogen protection, stirring, and at 85–95°C for 6–8 hours. After the reaction was completed, the mixture was cooled to room temperature, and concentrated hydrochloric acid was slowly added dropwise with stirring to adjust the pH of the system to 2–3, allowing the white solid to precipitate. The solid and liquid were then separated, and the obtained solid was washed with anhydrous ethanol to remove residual Na. + The unreacted sodium hydrosulfide was washed and dried to obtain modified 1-hydroxyethylidene-1,1-diphosphoric acid; the molar ratio of 1-hydroxyethylidene-1,1-diphosphoric acid to sodium hydrosulfide was 1:1.3-1.5. In the above steps, solid-liquid separation is performed by suction filtration, washing is generally performed twice, and drying is carried out under vacuum at 60℃ and -0.09MPa for 2-4 hours. The slow addition of sodium hydrosulfide is done by preparing an aqueous solution of sodium hydrosulfide and adding it dropwise at a rate of 1-2 drops / second. The mass concentration of the sodium hydrosulfide aqueous solution is generally 20-90%. The advantage of slow addition of sodium hydrosulfide is that it promotes complete reaction. The concentrated hydrochloric acid is also slowly added at a rate of 1-2 drops / second. Slow addition of hydrochloric acid prevents volatilization. The concentration of concentrated hydrochloric acid is generally 35%-37%. The equation for the reaction between HEDP and NaHS is: HEDP(2P-OH) + NaHS →HS-HEDP(1P-SH) + NaOH + H2O.
[0012] The modified cellulose is obtained through the following steps: (1) Disperse the powdered cellulose in ethanol, stir and slowly add sodium hydroxide at 30–35℃. After the sodium hydroxide is added, continue stirring for 25–30 min. Then, fully activate the cellulose at 30–35℃. After the activation reaction is complete, the activated cellulose system is obtained. The molar ratio of cellulose to sodium hydroxide is 1:1.1–1.3. In the above steps, the activation time is generally 1-1.5 hours. Sodium hydroxide is added slowly in three portions, with an interval of 3-5 minutes between each addition. The advantage of adding it in portions is that it facilitates the full progress of the substitution reaction. The reaction equation for this step is: Cell-OH + NaOH → Cell-ONa + H2O.
[0013] (2) The ethanol solution of chloroacetic acid was slowly added dropwise to the activated cellulose system obtained in step (1) under stirring and temperature conditions of 60–65℃. After the addition was completed, the chloroacetic acid and cellulose were allowed to react fully under stirring and temperature conditions of 60–65℃. After the reaction was completed, a reaction system containing sodium carboxymethyl cellulose was obtained; the molar ratio of chloroacetic acid to activated cellulose was 1.1–1.3:1. In this step, the concentration of the chloroacetic acid ethanol solution is generally 50-90%, and the slow dripping rate is 1-2 drops / second. The slow dripping allows for a more complete reaction. The time for chloroacetic acid and activated cellulose to react completely is generally 4-5 hours. The advantage of dissolving chloroacetic acid in ethanol and adding it dropwise is that the formation of a mixture is conducive to the reaction. The reaction equation for this step is: Cell-ONa + ClCH2COOH → Cell-O-CH2COONa + NaCl.
[0014] (3) Cool the reaction system containing sodium carboxymethyl cellulose to room temperature, slowly add concentrated hydrochloric acid dropwise while stirring, adjust the pH of the reaction system to 2–3, continue stirring until the reaction is complete, and let the product settle after the reaction is complete; after settling, perform solid-liquid separation to obtain the solid. In this step, concentrated hydrochloric acid is added slowly at a rate of 1–2 drops / second, with a concentration of 35%–37%. The advantage of slow addition is to prevent the volatilization of the concentrated hydrochloric acid. Stirring is continued until the reaction is complete, typically for a period of time. 10-15 min, the settling time is generally 30-35 min; solid-liquid separation is performed by vacuum filtration; The reaction equation for this step is: Cell-O-CH2COONa + HCl → Cell-O-CH2COOH + NaCl.
[0015] (4) The solid obtained in step (3) is first washed with deionized water to remove the residual NaCl, NaOH and chloroacetic acid on the solid. Then the solid is dried and pulverized in sequence. After pulverization, modified cellulose is obtained. Drying is generally carried out under vacuum conditions of 60℃ and -0.09MPa, and the drying time is generally 2-4 hours; the modified cellulose after pulverization is generally above 80 mesh.
[0016] The dispersant is a mixture of one or more of polymaleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid copolymer and polyaspartic acid in any mass ratio.
[0017] The nonionic surfactant is one or a mixture of two of alkyl glucosides and propylene glycol block polyethers in any mass ratio.
[0018] The synergist is any one or a mixture of two or more of sodium ethylenediaminetetramethylenephosphonate, benzotriazole (BTA), and sodium dodecylbenzenesulfonate (SDBS) in any mass ratio.
[0019] To achieve the second objective of the invention, the preparation method of the composite snow melting agent corrosion inhibitor provided by the present invention is as follows: the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water are mixed evenly according to the ratio to obtain the composite snow melting agent corrosion inhibitor.
[0020] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0021] 1. The composite de-icing agent corrosion inhibitor of the present invention has a good protective effect on metal products and a high effective concentration. The composite de-icing agent corrosion inhibitor has good stability and can stably protect metal products in an environment of -20℃.
[0022] First, this invention uses a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) as the passivating agent, which has a synergistic effect. 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) introduces thiol groups (-SH) by thioreplacing the P-OH or C-OH bonds in the molecule through a thioreaction, which significantly enhances its adsorption capacity on metal surfaces (the synergistic effect of thiol group binding to metal coordination bonds + phosphonic acid group chelation). Modifying cellulose by reacting it with chloroacetic acid to introduce -COOH groups improves the adsorption of corrosion inhibitors and enhances the film-forming ability on metal surfaces. Secondly, highly branched polyamide amines (PAMAMs) possess a precisely controllable three-dimensional structure, abundant surface functional groups (such as -NH2 and -COOH), and internal cavities, exhibiting excellent adsorption and corrosion inhibition properties. The -NH2 in the dendritic compounds is protonated in acidic media (-NH3). + This enhances the adsorption of corrosion inhibitors; the internal cavity structure can load synergist molecules (such as benzotriazole) to achieve synergistic corrosion inhibition.
[0023]
[0024] Finally, the nonionic surfactant of this invention is an alkyl glucoside and / or propylene glycol block polyether, which can maintain the stability of each component in the composite de-icing agent corrosion inhibitor and extend its service life.
[0025] 2. The composite de-icing agent corrosion inhibitor of this invention can effectively protect metal products and has a good effect on dispersing metal ions. The composite de-icing agent corrosion inhibitor of this invention does not coagulate with the de-icing agent, and after dissolving in water, the solution is clear and does not easily form insoluble substances, thus maintaining the original stability of the de-icing agent.
[0026] 3. The composite de-icing agent corrosion inhibitor of the present invention can be applied to the protection of related equipment such as roads, bridges, and airports, and can be used in environments with large pH fluctuations, such as -20℃. Detailed Implementation
[0027] To enable those skilled in the art to better understand the technical solutions of this invention, the technical solutions in the embodiments of this invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of this invention. Example 1
[0028] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 20% modified passivating agent, 10% dispersant, 10% nonionic surfactant, 10% synergist, and the remainder is deionized water.
[0029] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0030] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:2; the dispersant is a mixture of polymaleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid copolymer, and polyaspartic acid in a mass ratio of 1:2:3; the nonionic surfactant is a mixture of alkyl glucoside and propylene glycol block polyether in a mass ratio of 1:1; and the synergist is a mixture of sodium ethylenediaminetetramethylenephosphonate, benzotriazole, and sodium dodecylbenzenesulfonate in a mass ratio of 1:1:2.
[0031] The preparation method of the above-mentioned modified 1-hydroxyethylidene-1,1-bisphosphonic acid (HEDP) is as follows: 1-Hydroxyethylidene-1,1-diphosphoric acid (HEDP) was mixed with ethanol, and then a 50% sodium hydrosulfide aqueous solution was slowly added dropwise at a rate of 2 drops / second under nitrogen protection, stirring, and at 25°C. After the addition was complete, the reaction was carried out for 8 hours under nitrogen protection, stirring, and at 85°C. After the reaction was completed, the mixture was cooled to room temperature, and the pH of the system was adjusted to 2–3 by slowly adding 35% concentrated hydrochloric acid at a rate of 2 drops / second. After the pH was adjusted, the mixture was allowed to stand to allow the white solid to precipitate. After the white solid had precipitated, it was filtered, and the resulting solid was washed twice with anhydrous ethanol to remove residual sodium. + The mixture was washed with sodium hydrosulfide and then vacuum dried for 4 hours at 60°C and -0.09 MPa to obtain modified 1-hydroxyethylidene-1,1-diphosphoric acid. The molar ratio of 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) to sodium hydrosulfide was 1:1.1. The amount of ethanol used was to completely dissolve 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) to a minimum. Considering the benefits of improving the flowability of the system, the amount of ethanol can be appropriately increased. The amount of ethanol is generally 6-8 times the molar amount of 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP).
[0032] The preparation method of the above-mentioned modified cellulose is as follows: (1) Disperse the powdered cellulose in ethanol, stir and slowly add sodium hydroxide at 30°C. Add the sodium hydroxide in 3 portions, with an interval of 3-5 min between each addition. After the sodium hydroxide is added, continue stirring for 25-30 min. Then, activate the cellulose at 30°C for 1 hour. After the activation reaction is complete, the activated cellulose system is obtained. The molar ratio of cellulose to sodium hydroxide is 1:1.1. The amount of ethanol used is the minimum required to fully disperse the cellulose. Considering the benefits of improving the flowability of the system, the amount of ethanol can be appropriately increased. The amount of ethanol is generally 10-20 times the mass of cellulose.
[0033] (2) Under stirring and 60°C conditions, a 60% chloroacetic acid ethanol solution was slowly added dropwise to the activated cellulose system obtained in step (1) at a rate of 2 drops / s. After the addition was completed, the chloroacetic acid and the activated cellulose were allowed to react fully for 4–5 hours under stirring and 60°C conditions. After the reaction was completed, a reaction system containing sodium carboxymethyl cellulose was obtained. The molar ratio of activated cellulose to chloroacetic acid was 1:1.1.
[0034] (3) Cool the reaction system containing sodium carboxymethyl cellulose to room temperature, and add 35% concentrated hydrochloric acid dropwise with stirring at a rate of 2 drops / s to adjust the pH of the reaction system to 2–3. After the addition is complete, continue stirring the reaction. After the reaction is complete (10-15 min), let it stand for 30 min to allow the product to precipitate completely. After standing, filter the mixture to obtain the solid. (4) The solid obtained in step (3) is first washed with deionized water to remove the residual NaCl, NaOH and chloroacetic acid on the solid. Then, the solid is vacuum dried for 4 hours at a temperature of 60℃ and a pressure of -0.09MPa. After drying, the solid is pulverized to a mesh size of 80 or higher to obtain modified cellulose. Example 2
[0035] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 15% modified passivating agent, 15% dispersant, 9% nonionic surfactant, 12% synergist, and the remainder is deionized water.
[0036] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0037] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:1; the dispersant is a mixture of polymaleic anhydride and 2-acrylamide-2-methylpropanesulfonic acid copolymer in a mass ratio of 1:2; the nonionic surfactant is a mixture of alkyl glucoside and propylene glycol block polyether in a mass ratio of 1:3; and the synergist is a mixture of sodium ethylenediaminetetramethylenephosphonate and benzotriazole in a mass ratio of 1:1.
[0038] The preparation method of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) is basically the same as that in Example 1, except that the molar ratio of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) to sodium hydrosulfide in this example is 1:1.2.
[0039] The preparation method of modified cellulose is basically the same as that in Example 1, except that: the molar ratio of cellulose to sodium hydroxide in this example is 1:1.2; and the molar ratio of activated cellulose to chloroacetic acid is 1:1.2. Example 3
[0040] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 16% modified passivating agent, 14% dispersant, 7% nonionic surfactant, 11% synergist, and the remainder is deionized water.
[0041] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0042] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:1; the dispersant is a mixture of polymaleic anhydride and polyaspartic acid in a mass ratio of 1:1; the nonionic surfactant is a mixture of alkyl glucoside and propylene glycol block polyether in a mass ratio of 1:1; and the synergist is a mixture of sodium ethylenediaminetetramethylenephosphonate and sodium dodecylbenzenesulfonate in a mass ratio of 1:2.
[0043] The preparation method of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) is basically the same as that in Example 1, except that the molar ratio of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) to sodium hydrosulfide in this example is 1:1.3.
[0044] The preparation method of modified cellulose is basically the same as that in Example 1, except that: the molar ratio of cellulose to sodium hydroxide in this example is 1:1.3; and the molar ratio of activated cellulose to chloroacetic acid is 1:1.3. Example 4
[0045] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 17% modified passivating agent, 13% dispersant, 6% nonionic surfactant, 11.5% synergist, and the remainder is deionized water.
[0046] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0047] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:2; the dispersant is a mixture of 2-acrylamide-2-methylpropanesulfonic acid copolymer and polyaspartic acid in a mass ratio of 1:3; the nonionic surfactant is a mixture of alkyl glucoside and propylene glycol block polyether in a mass ratio of 1:2; and the synergist is a mixture of benzotriazole and sodium dodecylbenzenesulfonate in a mass ratio of 1:1.
[0048] The preparation method of the modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) is the same as that in Example 1.
[0049] The preparation method of the modified cellulose is the same as that in Example 1. Example 5
[0050] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 16% modified passivating agent, 11% dispersant, 9% nonionic surfactant, 10.5% synergist, and the remainder is deionized water.
[0051] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0052] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP), modified cellulose and polyamide amine (PAMAM) in a mass ratio of 2:2.5:2; the dispersant is polymaleic anhydride; the nonionic surfactant is alkyl glucoside; and the synergist is sodium ethylenediaminetetramethylenephosphonate.
[0053] The preparation method of the modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) is the same as that in Example 2.
[0054] The preparation method of the modified cellulose described above is the same as that in Example 2. Example 6
[0055] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 19% modified passivating agent, 12% dispersant, 8% nonionic surfactant, 11.5% synergist, and the remainder is deionized water.
[0056] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0057] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP), modified cellulose and polyamide amine (PAMAM) in a mass ratio of 2:2.5:1; the dispersant is 2-acrylamide-2-methylpropanesulfonic acid copolymer; the nonionic surfactant is propylene glycol block polyether; and the synergist is benzotriazole.
[0058] The preparation method of the modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) is the same as that in Example 3.
[0059] The preparation method of the modified cellulose described above is the same as that in Example 3. Example 7
[0060] The components of the composite de-icing agent corrosion inhibitor, by mass percentage, are as follows: The composition consists of 20% modified passivating agent, 10% dispersant, 10% nonionic surfactant, 10% synergist, and the remainder is deionized water.
[0061] Take each component according to the ratio, and then mix the modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water evenly to obtain the composite snow melting agent special corrosion inhibitor.
[0062] In the above components, the modified passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP), modified cellulose and polyamide amine (PAMAM) in a mass ratio of 2:3:2; the dispersant is polyaspartic acid; the nonionic surfactant is alkyl glucose; and the synergist is sodium dodecylbenzenesulfonate.
[0063] The preparation method of the modified 1-hydroxyethylidene-1,1-diphosphoric acid (HEDP) is the same as that in Example 1.
[0064] The preparation method of the modified cellulose is the same as that in Example 1. Comparative Example 1
[0065] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 1; the difference lies in the passivating agent. The passivating agent in Example 1 is a modified passivating agent, a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:2; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:2. Comparative Example 2
[0066] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 2; the difference lies in the passivating agent. The passivating agent in Example 2 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:1; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:1. Comparative Example 3
[0067] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 3; the difference lies in the passivating agent. The passivating agent in Example 3 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:1; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:1. Comparative Example 4
[0068] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 4; the difference lies in the passivating agent. The passivating agent in Example 4 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:2; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2:2. Comparative Example 5
[0069] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 5; the difference lies in the passivating agent. The passivating agent in Example 5 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2.5:2; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2.5:2. Comparative Example 6
[0070] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 6; the difference lies in the passivating agent. The passivating agent in Example 6 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2.5:1; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:2.5:1. Comparative Example 7
[0071] The composition, content of each component, and preparation method of the composite de-icing agent corrosion inhibitor in this comparative example are basically the same as those in Example 7; the difference lies in the passivating agent. The passivating agent in Example 7 is a modified passivating agent, which is a mixture of modified 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), modified cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:2; while the passivating agent in this comparative example is a mixture of 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP), cellulose, and polyamide amine (PAMAM) in a mass ratio of 2:3:2.
[0072] Referring to GB / T 18175-2014 Method for Determination of Corrosion Rate of Carbon Steel, the corrosion inhibitors prepared in Examples 1-7 and Comparative Examples 1-7 were mixed with chlorine-containing composite de-icing agents to prepare aqueous solutions of chlorine-containing de-icing agents with a mass concentration of 29%. The chlorine-containing composite de-icing agents were also prepared to a mass concentration of 29%, resulting in 15 chlorine-containing test solutions. In the aqueous solutions of chlorine-containing de-icing agents containing corrosion inhibitors, the corrosion inhibitor accounted for 0.5% of the mass of the chlorine-containing composite de-icing agent, and the chlorine-containing composite de-icing agent contained 80% sodium chloride and 20% calcium chloride. The corrosion inhibitors prepared in Examples 1-7 and Comparative Examples 1-7 were mixed with chlorine-free composite de-icing agents to prepare chlorine-free de-icing agent aqueous solutions with a mass concentration of 29%. The chlorine-free composite de-icing agents were also prepared to a mass concentration of 29%, resulting in 15 chlorine-free test solutions. In the chlorine-free de-icing agent aqueous solutions containing corrosion inhibitors, the corrosion inhibitor accounted for 0.5% of the mass of the chlorine-free composite de-icing agent. The chlorine-free composite de-icing agent contained 30% sodium formate, 30% potassium formate, and 40% potassium acetate. Carbon steel sheets were immersed in the above 15 chlorine-containing test solutions to determine the corrosion rate under conditions of 25℃ and -20℃. The test results are shown in Tables 1 and 2. The carbon steel sheets were also immersed in the above 15 chlorine-free test solutions to determine the corrosion rate under conditions of 25℃ and -20℃. The test results are shown in Tables 3 and 4.
[0073]
[0074]
[0075]
[0076]
[0077] The test results in Tables 1 and 2 show that Example 1 demonstrates excellent performance in protecting metals from corrosion at 25°C, achieving good results even with low dosage. It also shows good corrosion protection at -20°C, exhibiting a wide applicable temperature range. Example 1 exhibits the best performance. The corrosion inhibition effect of Example 1 is significantly better than that of Comparative Example 1, proving that the modified passivating agent used in this invention has a significant synergistic effect, contributing to improved corrosion inhibition. The test results comparing Examples 1 and 7 show that using a variety of mixed nonionic surfactants, dispersants, and synergists can significantly reduce the corrosion rate of carbon steel, which is beneficial for metal protection.
[0078] As can be seen from the test results in Tables 3 and 4, the corrosion inhibitor also exhibits excellent anti-corrosion effect in the chlorine-free composite de-icing agent, especially the effect of Example 1 is particularly outstanding. In summary, whether it is a chlorine-containing composite de-icing agent or a chlorine-free composite de-icing agent, the corrosion inhibitor containing the modified passivator has a very obvious synergistic effect on anti-corrosion.
[0079] Although the present invention has been described in detail by way of preferred embodiments, the present invention is not limited thereto. Various equivalent modifications or substitutions can be made to the embodiments of the present invention by those skilled in the art without departing from the spirit and essence of the invention, and such modifications or substitutions should all be within the scope of the present invention. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should also be covered within the protection scope of the present invention. Therefore, the protection scope of the present invention should be determined by the scope of the claims.
Claims
1. A corrosion inhibitor specifically for composite de-icing agents, characterized in that: The components, in terms of mass percentage, include: 15%-20% modified passivating agent, 10%-15% dispersant, 5%-10% nonionic surfactant, 10%-12% synergist, and the remainder is deionized water.
2. The composite de-icing agent corrosion inhibitor as described in claim 1, characterized in that: The passivating agent is a mixture of modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose, and polyamide amine.
3. The composite de-icing agent corrosion inhibitor as described in claim 2, characterized in that: The mass ratio of the modified 1-hydroxyethylidene-1,1-diphosphoric acid, modified cellulose, and polyamide amine is 2:2-3:1-2.
4. The composite de-icing agent corrosion inhibitor as described in claim 2 or 3, characterized in that: The modified 1-hydroxyethylidene-1,1-diphosphoric acid is prepared by the following steps: 1-Hydroxyethylidene-1,1-diphosphoric acid was mixed with ethanol, and sodium hydrosulfide was slowly added under nitrogen protection, stirring, and at 25°C. After the addition of sodium hydrosulfide (NaHS) was complete, the reaction was carried out under nitrogen protection, stirring, and at 85–95°C for 6–8 hours. After the reaction was completed, the mixture was cooled to room temperature, and concentrated hydrochloric acid was slowly added dropwise with stirring to adjust the pH of the system to 2–3, allowing the white solid to precipitate. The solid and liquid were then separated, and the obtained solid was washed with anhydrous ethanol to remove residual Na. + The unreacted sodium hydrosulfide was washed and dried to obtain modified 1-hydroxyethylidene-1,1-diphosphoric acid.
5. The composite de-icing agent corrosion inhibitor as described in claim 2 or 3, characterized in that: The modified cellulose is obtained through the following steps: (1) Disperse the powdered cellulose in ethanol, stir and slowly add sodium hydroxide at 30–35℃. After the sodium hydroxide is added, continue stirring for 30–35 min. Then, fully activate the cellulose at 30–35℃. After the activation reaction is complete, the activated cellulose system is obtained. (2) Under stirring and a temperature of 60–65℃, the ethanol solution of chloroacetic acid was slowly added dropwise to the activated cellulose system obtained in step (1). After the addition was completed, the chloroacetic acid and cellulose were allowed to react fully under stirring and a temperature of 60–65℃. After the reaction was completed, a reaction system containing sodium carboxymethyl cellulose was obtained. (3) Cool the reaction system containing sodium carboxymethyl cellulose to room temperature, slowly add concentrated hydrochloric acid dropwise while stirring, adjust the pH of the reaction system to 2–3, continue stirring until the reaction is complete, and let the product settle after the reaction is complete; after settling, perform solid-liquid separation to obtain the solid. (4) The solid obtained in step (3) is first washed with deionized water to remove the residual NaCl, NaOH and chloroacetic acid on the solid. Then the solid is dried and pulverized in sequence. After pulverization, modified cellulose is obtained.
6. The preparation method of the composite de-icing agent corrosion inhibitor as described in claim 1, characterized in that: The dispersant is a mixture of one or more of polymaleic anhydride, 2-acrylamide-2-methylpropanesulfonic acid copolymer and polyaspartic acid in any mass ratio.
7. The preparation method of the composite de-icing agent corrosion inhibitor as described in claim 1, characterized in that: The nonionic surfactant is one or a mixture of two of alkyl glucosides and propylene glycol block polyethers in any mass ratio.
8. The preparation method of the composite de-icing agent corrosion inhibitor as described in claim 1, characterized in that: The synergist is any one or a mixture of two or more of sodium ethylenediaminetetramethylenephosphonate, benzotriazole and sodium dodecylbenzenesulfonate in any mass ratio.
9. A method for preparing a corrosion inhibitor specifically for composite de-icing agents according to any one of claims 1-8, characterized in that: The modified passivating agent, dispersant, nonionic surfactant, synergist and deionized water are mixed evenly according to the specified ratio to obtain a composite de-icing agent-specific corrosion inhibitor.