MXene composite corrosion inhibitor and preparation method and application thereof

Abstract

The present application relates to the technical field of metal corrosion inhibitor, in particular to a MXene composite corrosion inhibitor, a preparation method and application thereof.The preparation method of the MXene composite corrosion inhibitor is as follows: MXene powder and hexamethylene diamine are mixed and then added into anhydrous ethanol for stirring, and ultrasonic treatment to obtain a MXene powder mixture; the MXene powder mixture is mixed with double distilled water, and reacted in a reaction kettle to obtain a MXene mixture solution, which is then mixed with an additive and subjected to ultrasonic treatment to obtain a MXene composite corrosion inhibitor intermediate solution; the MXene composite corrosion inhibitor intermediate solution is mixed with double distilled water, and then hydrochloric acid solution is added to obtain the MXene composite corrosion inhibitor.The preparation method is simple, low in cost, and the obtained MXene composite corrosion inhibitor can not only realize efficient and rapid etching of zinc element in hot galvanizing layer, but also effectively prevent etching of iron element in steel plate.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal corrosion inhibitor, in particular to a MXene composite corrosion inhibitor and a preparation method and application thereof. BACKGROUND

[0002] Hot-dip galvanized sheet is a kind of steel sheet coated with a layer of hot-dip galvanized layer by hot-dip galvanizing process. Through the reaction and diffusion between iron and zinc, the hot-dip galvanized layer is uniform and dense, and has strong bonding force with the steel sheet. Compared with other metal protection methods, the hot-dip galvanized layer has incomparable advantages in durability, maintenance-free and economy, and can greatly delay the corrosion of the steel sheet, and is widely used in automobiles, ships, electrical appliances and other equipment. However, when these equipment reaches the service life, due to the uniform and dense hot-dip galvanized layer and the strong bonding force, it is difficult for zinc element to separate from the steel sheet, and the hot-dip galvanized sheet has high recycling cost and low zinc recovery rate, and recycling is difficult.

[0003] Generally, the recycling of hot-dip galvanized sheet is realized by the method of hydrochloric acid etching. However, when the hot-dip galvanized layer is recycled by using hydrochloric acid, the internal steel sheet will inevitably be etched. How to realize efficient etching of the galvanized layer and ensure the corrosion inhibition of the internal steel sheet during the recycling of the hot-dip galvanized sheet has become a difficult problem. At present, organic corrosion inhibitors with dezincification effect have been developed on the market, but there are problems such as long etching time (about 1h) of hot-dip galvanized sheet, poor iron corrosion inhibition effect (the remaining iron content in steel is about 60%), low zinc recovery rate (below 95%), and high cost. Therefore, it is urgent to provide a steel corrosion inhibitor with high zinc recovery rate for recycling of hot-dip galvanized sheet. SUMMARY

[0004] In view of the problems of long etching time, low zinc recovery rate, poor steel corrosion inhibition effect and high cost of the existing corrosion inhibitors applied to the recycling of hot-dip galvanized sheet, the present application provides a MXene composite corrosion inhibitor and a preparation method and application thereof.

[0005] In the first aspect, the present application provides a preparation method of a MXene composite corrosion inhibitor, comprising the following steps:

[0006] (1) mixing MXene powder and hexamethylene diamine according to a mass ratio of 1:5-10, then adding into anhydrous ethanol and stirring, and ultrasonic treatment for 30-60min to obtain a MXene powder mixture;

[0007] (2) mixing the MXene powder mixture obtained in step (1) with 10-15L double distilled water, and reacting in a reaction kettle at a temperature of 150-180℃ for 2-5h to obtain a MXene mixed solution, then mixing the MXene mixed solution with an additive according to a mass ratio of 2-5:1, and performing secondary ultrasonic treatment for 30-40min to obtain a MXene composite corrosion inhibitor intermediate solution;

[0008] (3) Mix the MXene composite corrosion inhibitor intermediate solution with double distilled water at a volume ratio of 1:14-20, and then add a hydrochloric acid solution with a concentration of 5.0%-10.0% to obtain the MXene composite corrosion inhibitor;

[0009] Wherein, the mass volume ratio of MXene powder and anhydrous ethanol in step (1) is 10-30 g: 2-5 L;

[0010] In step (2), the additive is selected from one or more of 8-hydroxyquinoline, 2-mercaptobenzothiazole, 5-amino-1,3,4-thiadiazole-2-thiol, calcium phosphate, cerium nitrate and sodium molybdate;

[0011] In step (3), the volume ratio of the MXene composite corrosion inhibitor intermediate solution to the hydrochloric acid solution is 1:20-40.

[0012] Furthermore, the preparation method of MXene powder in step (1) is as follows: lithium fluoride is mixed with a hydrochloric acid solution with a concentration of 36%, Ti3AlC2 is added, ultrasonic and magnetic stirring are performed successively, and then double-distilled water is added for washing. After washing, the pH of the solution is increased to 6 and centrifuged. The upper clear liquid is the initial MXene solution. The initial MXene solution is mixed with anhydrous ethanol for reaction, and then double-distilled water is added for washing, and freeze-drying is performed to obtain MXene powder.

[0013] Furthermore, the mass volume ratio of lithium fluoride to hydrochloric acid solution is 20-50g:3-10L.

[0014] Furthermore, the mass ratio of lithium fluoride to Ti3AlC2 is 2-5:15-30.

[0015] Furthermore, the ultrasonic time is 20-30 minutes; the magnetic stirring temperature is 40° C., and the time is 12-24 hours.

[0016] Furthermore, the MXene initial solution was mixed with anhydrous ethanol in a volume ratio of 3-5:1 and reacted at 50-60 °C for 1-5 h.

[0017] Furthermore, the additive in step (2) is 8-hydroxyquinoline, 2-mercaptobenzothiazole or cerium nitrate.

[0018] In a second aspect, the present invention provides a MXene composite corrosion inhibitor prepared by the above preparation method.

[0019] In a third aspect, the present invention provides an application of the above-mentioned MXene composite corrosion inhibitor for corrosion and dezincification of hot-dip galvanized sheet.

[0020] Furthermore, the etching and dezincification time is 12 minutes.

[0021] The present application has the advantages that:

[0022] The present application provides a preparation method of MXene composite corrosion inhibitor, which is simple to operate, low in raw material cost, and has the characteristics of more active sites, larger active area and easy adsorption on the surface of steel, so that the obtained MXene composite corrosion inhibitor can not only realize the corrosion of zinc element in hot galvanizing layer, but also effectively hinder the corrosion of iron element in steel plate, and the corrosion time is about one fifth of that of the existing organic corrosion inhibitor, which is time-saving and efficient. Energy spectrum detection shows that under the same conditions, compared with hydrochloric acid solution, the use of the MXene composite corrosion inhibitor provided by the present application for hot dip galvanizing plate corrosion greatly reduces the iron element corrosion amount, and the zinc element corrosion amount is equivalent to the effect of hydrochloric acid corrosion, which shows that the MXene composite corrosion solution greatly reduces the corrosion of steel plate while corroding zinc, and effectively realizes the corrosion inhibition of iron element. DETAILED DESCRIPTION

[0023] In order to enable the personnel in the technical field to better understand the technical solutions in the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the scope of protection of the present application.

[0024] Embodiment 1

[0025] A preparation method of MXene composite corrosion inhibitor, comprising the following steps:

[0026] 1. Preparation of MXene powder

[0027] (1) 20 g of lithium fluoride powder is mixed with 3 L of hydrochloric acid solution (36% by weight) to obtain a clear solution, 150 g of MAX (Ti3AlC2) is added and ultrasonic stirring is performed for 20 min, then magnetic stirring reaction is performed at a temperature of 40℃ for 12 h, after the reaction is completed, double distilled water is added for cleaning until the pH of the solution after cleaning is increased to 6, then centrifugal treatment is performed, and the upper clear liquid is taken to obtain an MXene initial solution;

[0028] (2) The MXene initial solution is mixed with anhydrous ethanol at a volume ratio of 5:1, and a reaction is performed at a temperature of 50℃ for 1 h to obtain an MXene secondary solution;

[0029] (3) The MXene secondary solution is cleaned with double distilled water and freeze-dried for 24 h to obtain a product MXene powder.

[0030] 2. Preparation of MXene composite corrosion inhibitor

[0031] (1) Weigh 10 g of MXene powder and 50 g of hexamethylenediamine, mix them in a mass ratio of 1:5, then add them to 2 L of anhydrous ethanol solution, stir for 30 min to obtain a mixed solution, and ultrasonicate for 30 min to obtain a MXene powder mixed solution;

[0032] (2) Add 10 L of double-distilled water to the MXene powder mixture, pour it into a reactor, raise the temperature to 180 ° C at a rate of 2 ° C / min, and react for 3 h to obtain a MXene mixed solution. The MXene mixed solution is mixed with 2-mercaptobenzothiazole and subjected to a secondary ultrasonic treatment. The ultrasonic time is 40 min, and the mass ratio of the MXene mixed solution to 2-mercaptobenzothiazole is 4:1 to obtain a MXene composite corrosion inhibitor intermediate solution;

[0033] (3) Measure 5 L of the MXene composite corrosion inhibitor intermediate solution, add 70 L of double-distilled water to dilute and mix, and then add 150 L of 10.0% hydrochloric acid to obtain the MXene composite corrosion inhibitor.

[0034] Example 2

[0035] A method for preparing a MXene composite corrosion inhibitor comprises the following steps:

[0036] 1. Preparation of MXene powder

[0037] (1) 50 g of lithium fluoride powder was mixed with 5 L of hydrochloric acid solution (36% concentration) to obtain a clear solution, into which 300 g of MAX (Ti3AlC2) was poured and ultrasonically stirred for 20 min. After the MAX phase was evenly dispersed, magnetic stirring was performed at 40 °C for 18 h. After the reaction was completed, double distilled water was added for washing until the pH of the solution increased to 6.5 after washing. The solution was then centrifuged and the supernatant was taken to obtain the initial MXene solution.

[0038] (2) The MXene initial solution was mixed with anhydrous ethanol at a volume ratio of 5:1 and reacted at 60 °C for 1 h to obtain a MXene secondary solution;

[0039] (3) The MXene secondary solution was washed with double distilled water and freeze-dried for 18 h to obtain the product MXene powder.

[0040] 2. Preparation of MXene composite corrosion inhibitor

[0041] (1) Weigh 20 g of MXene powder and 200 g of hexamethylenediamine, mix them in a mass ratio of 1:10, then add them to 5 L of anhydrous ethanol solution, stir for 30 min to obtain a mixed solution, and ultrasonicate for 60 min to obtain a MXene powder mixed solution;

[0042] (2) Add 15 L of double-distilled water to the MXene powder mixture, pour it into a reactor, raise the temperature to 150 ° C at a rate of 2 ° C / min, and react for 2 h to obtain a MXene mixed solution. The MXene mixed solution is mixed with 8-hydroxyquinoline and subjected to a secondary ultrasonic treatment. The ultrasonic time is 30 min. The mass ratio of the MXene mixed solution to 2-mercaptobenzothiazole is 2:1 to obtain a MXene composite corrosion inhibitor intermediate solution.

[0043] (3) Measure 5 L of the MXene composite corrosion inhibitor intermediate solution, add 100 L of double-distilled water to dilute and mix, and then add 200 L of 5.0% hydrochloric acid to obtain the MXene composite corrosion inhibitor.

[0044] Example 3

[0045] A method for preparing a MXene composite corrosion inhibitor comprises the following steps:

[0046] 1. Preparation of MXene powder

[0047] (1) 50 g of lithium fluoride powder was mixed with 10 L of hydrochloric acid solution (36% concentration) to obtain a clear solution, 300 g of MAX (Ti3AlC2) was poured into it, and ultrasonic stirring was carried out for 20 min. After the MAX phase was evenly dispersed, magnetic stirring was carried out at 40 °C for 24 h. After the reaction was completed, double distilled water was added for washing until the pH of the solution increased to 6 after washing. Then, the solution was centrifuged and the supernatant was taken to obtain the MXene initial solution.

[0048] (2) The MXene initial solution was mixed with anhydrous ethanol in a volume ratio of 5:1 and reacted at 60 °C for 5 h to obtain a MXene secondary solution;

[0049] (3) The MXene secondary solution was washed with double distilled water and freeze-dried for 24 h to obtain the product MXene powder.

[0050] 2. Preparation of MXene composite corrosion inhibitor

[0051] (1) Weigh 30 g of MXene powder and 150 g of hexamethylenediamine, mix them in a mass ratio of 1:5, then add them to 5 L of anhydrous ethanol solution, stir for 30 min to obtain a mixed solution, and ultrasonicate for 60 min to obtain a MXene powder mixed solution;

[0052] (2) In the MXene powder mixed solution, 15 L of double distilled water was added, poured into the reaction kettle, and increased to 160°C at a rate of 2°C / min for 5 h to obtain a MXene mixed solution. The MXene mixed solution was mixed with cerium nitrate and subjected to secondary ultrasonic treatment for 30 min. The mass ratio of the MXene mixed solution to 2-mercaptobenzothiazole was 5:1 to obtain a MXene composite inhibitor intermediate solution;

[0053] (3) 5 L of the MXene composite inhibitor intermediate solution was measured, 100 L of double distilled water was added for dilution and mixing, and 200 L of 5.0% hydrochloric acid was added to obtain the MXene composite inhibitor.

[0054] Experimental Example 1

[0055] Four pieces of hot-dip galvanized plates of the same size were immersed in equal amounts of the MXene composite inhibitors prepared in Examples 1-3, respectively, and immersed for 12 min to complete the recycling and reuse of the waste hot-dip galvanized plates. The hot-dip galvanized plates were taken out, and the contents of Fe, Zn, and Al immersed and leached by the MXene composite inhibitor were detected by inductively coupled plasma mass spectrometry (ICP). A 15% hydrochloric acid solution was used instead of the MXene composite inhibitor for a comparative test, and the test results are shown in Table 1.

[0056] Table 1 Comparison of Fe, Zn, and Al contents leached by the MXene composite inhibitors of Examples 1-3 and the hydrochloric acid solution

[0057]

[0058] From the results in Table 1, compared with the hydrochloric acid solution, the MXene composite inhibitor of Examples 1-3 greatly reduced the iron leaching amount after treating the waste hot-dip galvanized plates, while the zinc leaching amount was not significantly different, indicating that the MXene composite inhibitor can effectively leach zinc while greatly reducing the corrosion of the steel plate, thereby improving the recycling rate of the hot-dip galvanized plate.

[0059] Although the present application has been described in detail by preferred embodiments, the present application is not limited thereto. Various equivalent modifications and replacements can be made to the embodiments of the present application by those skilled in the art without departing from the spirit and essence of the present application, and these modifications and replacements shall be within the scope of the present application. Any person skilled in the art can easily think of changes or replacements within the technical range disclosed by the present application, and these changes or replacements shall be within the protection scope of the present application.

Claims

1. A method for preparing a MXene composite corrosion inhibitor, characterized in that: The steps include: (1) Mix MXene powder and hexamethylenediamine in a mass ratio of 1:5-10, add them to anhydrous ethanol, stir, and ultrasonicate for 30-60 minutes to obtain a MXene powder mixture; (2) The MXene powder mixture obtained in step (1) is mixed with 10-15 L of double distilled water, and the mixture is reacted in a reactor at a temperature of 150-180 ° C for 2-5 hours to obtain a MXene mixed solution. The MXene mixed solution and the additive are mixed in a mass ratio of 2-5:1 and then subjected to a secondary ultrasonic treatment for 30-40 minutes to obtain a MXene composite corrosion inhibitor intermediate solution; (3) Mix the MXene composite corrosion inhibitor intermediate solution and double distilled water in a volume ratio of 1:14-20, and then add a hydrochloric acid solution with a concentration of 5.0%-10.0% to obtain the MXene composite corrosion inhibitor; The preparation method of MXene powder in step (1) is as follows: lithium fluoride is mixed with a hydrochloric acid solution having a concentration of 36%, Ti3AlC2 is added, ultrasonic and magnetic stirring are performed successively, and then double-distilled water is added for washing. After washing, the pH of the solution is raised to 6 and centrifuged. The supernatant is the initial MXene solution. The initial MXene solution is mixed with anhydrous ethanol for reaction, and then double-distilled water is added for washing, and freeze-drying is performed to obtain MXene powder. In step (1), the mass volume ratio of lithium fluoride to hydrochloric acid solution is 20-50 g:3-10 L; In step (1), the mass ratio of lithium fluoride to Ti3AlC2 is 2-5:15-30; In step (1), the mass volume ratio of MXene powder to anhydrous ethanol is 10-30 g: 2-5 L; In step (2), the additive is selected from one or more of 8-hydroxyquinoline, 2-mercaptobenzothiazole, 5-amino-1,3,4-thiadiazole-2-thiol, calcium phosphate, cerium nitrate and sodium molybdate; In step (3), the volume ratio of the MXene composite corrosion inhibitor intermediate solution to the hydrochloric acid solution is 1:20-40.

2. The method for preparing a MXene composite corrosion inhibitor according to claim 1, wherein: The ultrasonic time is 20-30 minutes; the magnetic stirring temperature is 40°C and the time is 12-24 hours.

3. The method for preparing a MXene composite corrosion inhibitor according to claim 1, wherein: The MXene initial solution was mixed with anhydrous ethanol in a volume ratio of 3-5:1 and reacted at 50-60 °C for 1-5 h.

4. The method for preparing a MXene composite corrosion inhibitor according to claim 1, wherein: The additive in step (2) is 8-hydroxyquinoline, 2-mercaptobenzothiazole or cerium nitrate.

5. A MXene composite corrosion inhibitor prepared by the preparation method according to claim 1.

6. Use of the MXene composite corrosion inhibitor as claimed in claim 5 for corrosion and dezincification of hot-dip galvanized sheet.

7. The use according to claim 6, characterized in that The time for etching and dezincification is 12 minutes.

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