Environment-friendly organic metal corrosion inhibitor suitable for whole environment as well as preparation method and application of environment-friendly organic metal corrosion inhibitor
By using the environmentally friendly organometallic corrosion inhibitor prepared by passion fruit shell and Boluohui fruit pod extract, the corrosion problem of traditional corrosion inhibitors in acid and alkali environment is solved by forming multiple protective films, effectively protecting metal Al is achieved, and has the characteristics of environmental protection, safety and economicality.
Patent Information
- Application Number
- CN202411421583.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-12
- Publication Date
- 2025-03-04
AI Technical Summary
Traditional metal corrosion inhibitors contain toxic substances, which are easy to cause harm to the human body and the environment. At the same time, there are few types of corrosion inhibitors with good sustained release effects in acid and alkali media, making it difficult to effectively inhibit the corrosion of metal Al in the entire environment.
Using passion fruit shell extract and boloe pod extract as the main components, an environmentally friendly organometallic corrosion inhibitor is prepared by combining and adding additives such as triethanolamine, trisodium citrate, borax, organic phosphine compounds and ulotropine. The corrosion inhibitor effectively isolates the acid-base corrosion medium from the surface of metal Al by forming a multiple protective film, including an adsorption film, a precipitation film and a passivation film, and slows down corrosion.
This corrosion inhibitor significantly slows down the corrosion rate of metal Al in an acid-base environment, provides comprehensive protection, is non-toxic and low-cost, and is suitable for all Al alloys, without pollution after use, safe and convenient to use.
Abstract
Description
Technical Field
[0001] The present invention relates to a metal corrosion inhibitor and a preparation method and application thereof, and more specifically to an environmentally friendly organic metal corrosion inhibitor and a preparation method and application thereof, belonging to the technical field of corrosion inhibitors. Background Art
[0002] Corrosion inhibitor is a chemical substance used to prevent metal corrosion, and it plays an important role in various anti-corrosion methods. It only needs to be added in a small amount to significantly reduce the corrosion rate of metals. Compared with other anti-corrosion methods, corrosion inhibitors are easy to use, economical and effective, and widely used in industrial production and social life. In order to protect metal resources, reduce production accidents and product losses, and control environmental pollution, corrosion inhibitor technology should develop in the direction of environmental friendliness, low toxicity, safety, high efficiency, multi-component and universal.
[0003] At present, the output and usage of aluminum are second only to steel, ranking second among various metals. Aluminum has the characteristics of beautiful appearance, low cost, strong plasticity and light weight, so it is widely used in food processing, household appliances, construction, automobiles, ships, aerospace and other fields. When aluminum is exposed to the atmosphere and many aqueous media, a passivation film will quickly form, thereby improving its corrosion resistance. However, this passivation film is only relatively stable when the pH value of the medium is 5.0-8.5, and is easily corroded in acidic or alkaline environments. In order to inhibit the corrosion of Al, scientific researchers have conducted a lot of research on related corrosion inhibitors for Al and its alloys. Traditional corrosion inhibitors, such as chromates, nitrites and mercury salts, are highly toxic and easily cause serious pollution to the environment. They have been restricted or banned. Plant extracts are rich in compounds such as phenylpropanoids, terpenes, flavonoids, tannins and amino acids. These compounds can act as active centers to promote the adsorption of corrosion inhibitor molecules on the metal surface, thereby inhibiting metal corrosion. They are a natural green corrosion inhibitor. Plant corrosion inhibitors have been extensively studied both at home and abroad, fully proving that they have the characteristics of low environmental risk, wide availability, high corrosion inhibition efficiency and low cost, and can serve as an ideal substitute for toxic and expensive traditional corrosion inhibitors. Summary of the invention
[0004] The technical problem to be solved by the present invention is: in view of the fact that traditional metal corrosion inhibitors contain toxic substances, which are easy to cause harm to the human body and the environment, and there are few types of corrosion inhibitors with good sustained-release effects in both acidic and alkaline media, the present invention provides an environmentally friendly organic metal corrosion inhibitor suitable for all environments and a preparation method thereof, aiming to provide a metal corrosion inhibitor with good corrosion inhibition performance in both acidic and alkaline environments, and solve the corrosion problem of metal Al in all environments.
[0005] The technical scheme of the present invention is: an environmentally friendly organic metal corrosion inhibitor suitable for the whole environment, comprising the following steps: (1) preparing passion fruit shell extract a; (2) filtering the sample a, and concentrating the filtrate to obtain passion fruit shell extract b; (3) preparing an extract of Macleaya oleifera pods (including seeds in the pods); (4) preparing a compound liquid of passion fruit shell extract; (5) preparing an environmentally friendly organic metal corrosion inhibitor: compounding the extract of Macleaya oleifera pods (including seeds in the pods) with the compound liquid of passion fruit shell extract in a volume ratio of 5:1 to 1:1 to obtain an environmentally friendly organic metal corrosion inhibitor.
[0006] Preparation of passion fruit shell extract a in step (1): (a) washing and drying passion fruit shell material; (b) crushing passion fruit shell material; (c) mixing passion fruit shell powder with 1 mol / L H 2 SO 4 The reaction is carried out under the conditions of a solid-liquid ratio (g / mL) of 1:25 to 1:35, a mechanical stirring speed of 90 to 150 rpm, a reaction time of 8 to 10 h, and a reaction temperature of 70 to 90° C. After the reaction, passion fruit shell extract a is obtained.
[0007] The preparation of the extract of Macleaya hupensis pods (including the seeds in the pods) in step (3) includes: (a) washing and drying the Macleaya hupensis pods; (b) crushing the Macleaya hupensis pods; (c) performing an extraction reaction of the Macleaya hupensis pods: adding the Macleaya hupensis pod powder to V 甲醇 :V 1％盐酸 =1:1 extract, solid-liquid ratio of 1:30-1:60 (g / mL), ultrasonic extraction at 60-80°C for 2-4 hours, filtration, and concentration of the filtrate to obtain the Macleaya cordata pod extract.
[0008] The preparation of the passion fruit shell extract compound liquid in the step (4) comprises the following components in mass percentage: 20% to 25% of passion fruit shell extract a, 2% to 4% of passion fruit shell extract b, 8% to 10% of triethanolamine, 6% to 8% of trisodium citrate, 3% to 6% of borax, 1% to 2% of organic phosphine compounds, 3% to 5% of methenamine, and the rest is water. The mixture is slightly heated, fully dissolved in water, and stirred evenly to obtain the passion fruit shell extract compound liquid.
[0009] Beneficial effects of the present invention:
[0010] 1. The metal corrosion inhibitor of the present invention comprises lignin, glucose and gluconic acid in the passion fruit shell extract, and alkaloids in the Macleaya cordata pod extract. The O atoms and N atoms of the two macromolecules of lignin and alkaloids in the extract can coordinate with the d empty orbit of metal ions to form coordination bonds, and are adsorbed on the metal surface to form an adsorption film framework on the metal surface. The glucose and gluconic acid small molecules in the passion fruit shell extract coordinate with the d empty orbit of metal ions to form coordination bonds and are embedded in the adsorption film framework formed by lignin and alkaloids through the O atoms. However, since the content of glucose and gluconic acid in the extract is small, additional additives (triethanolamine, trisodium citrate, glucose and urotropine) need to be added to fill the adsorption film framework, thereby forming a dense adsorption film layer on the metal surface. At the same time, the organic phosphine compound can react with calcium and magnesium ions in water to form a chelate to form a precipitation film attached to the metal surface. Borax can react with oxygen ions in water to form a passivation film, which consumes dissolved oxygen and inhibits the diffusion of dissolved oxygen. Under the multiple protection and isolation of adsorption film, precipitation film and passivation film, the acid and alkali corrosive medium is isolated from the metal Al surface, thereby slowing down the corrosion of the metal Al in the acid and alkali medium;
[0011] 2. The present invention forms multiple protective films to isolate the corrosive medium from the metal surface, thereby protecting the metal from corrosion. Therefore, the corrosion inhibitor is suitable for all Al alloys;
[0012] 3. The present invention overcomes the shortcomings of most corrosion inhibitors, such as high price, high toxicity and environmental pollution. Passion fruit shell extract and Macleaya pod extract are prepared from passion fruit shell and Macleaya pod as raw materials, and synergistic additives such as triethanolamine, trisodium citrate, borax, organic phosphine compounds, hexamethylenetetramine and water are added to prepare an environmentally friendly organic metal corrosion inhibitor. The environmentally friendly organic metal corrosion inhibitor described in the present invention is non-toxic, low-cost, highly adaptable, and significantly inhibits the corrosion of acid and alkali on metal Al. It is pollution-free after use and is safe and convenient to use.
[0013] 4. The environmentally friendly organic metal corrosion inhibitor prepared by the present invention can simultaneously meet the use requirements in acid and alkali environments, can effectively slow down the corrosion rate of metal Al, and play a role in comprehensive protection of metals. At the same time, the plant extract components and non-toxic additives in the corrosion inhibitor can reduce the harm to the environment and human body, and have broad application prospects;
[0014] 5. All substances in the environmentally friendly organic metal corrosion inhibitor of the present invention are biodegradable and are environmentally friendly substances;
[0015] 6. The application of the environmentally friendly organic metal corrosion inhibitor described in the present invention is the application of the corrosion inhibitor in a metal aluminum acid-base medium. DETAILED DESCRIPTION
[0016] (I) Preparation of passion fruit shell extract A
[0017] 1. Washing and drying of passion fruit shell materials;
[0018] Passion fruit shells include passion fruit shells from all origins and all varieties. They should be rinsed clean with tap water, dried at room temperature or with forced air (≤40°C) to avoid carbonization of the passion fruit shells due to excessive temperature.
[0019] 2. Crushing of passion fruit shell materials;
[0020] The particle size of passion fruit shell material should be 120-150 μm. If the particle size is too small, there will be residues left in the product during the later filtration, and if the particle size is too large, it will be unfavorable for the extraction of effective ingredients from passion fruit shell.
[0021] 3. Under normal pressure, temperature 70-90℃, passion fruit shell powder and 1mol / LH 2 SO 4 The reaction is carried out under the condition of a solid-liquid ratio (g / mL) of 1:25 to 1:35, a mechanical stirring speed of 90 to 150 rpm, and a reaction time of 8 to 10 hours. After the reaction, passion fruit shell extract a is obtained.
[0022] (II) Preparation of passion fruit shell extract B
[0023] The obtained passion fruit shell extract a is filtered, and the filtrate is concentrated to obtain the passion fruit shell extract b.
[0024] (III) Preparation of Macleaya oleifera pod (including seeds in pod) extract
[0025] 1. Washing and drying of the fruit pods of Bo Luo Hui;
[0026] The fruit pods of Boletus oleraceus include the fruit pods of Boletus oleraceus from all origins and all varieties, and also include the branches and leaves of all varieties of Boletus oleraceus. They should be cleaned with tap water, and air-dried at room temperature or with forced air (≤40°C) to avoid carbonization of the materials due to excessive temperature.
[0027] 2. Crushing of the fruit pods of Bo Luo Hui;
[0028] The crushing particle size of the fruit pods of Macleaya hui (including the seeds in the fruit pods) is preferably 80 to 120 μm. If the particle size is too small, residues will be left in the product during the later filtration, and if the particle size is too large, it will be unfavorable for the extraction of bioactive substances in the fruit pods of Macleaya hui, and reduce the yield of the Macleaya hui extract.
[0029] 3. Extraction reaction of Macleaya oleifera pods
[0030] Put 5g of crushed Macleaya hupensis pod powder into a 500mL conical flask, add 150-300mL of extract (V 甲醇 :V 1％盐酸=1:1 (volume ratio), ultrasonic extraction at 60-80°C for 2-4 hours, filtration, and concentration of the filtrate to obtain the Macleaya cordata pod extract.
[0031] (IV) Preparation of passion fruit shell extract compound solution
[0032] The passion fruit shell extract compound liquid comprises the following components in percentage by mass: 20% to 25% of passion fruit shell extract a, 2% to 4% of passion fruit shell extract b, 8% to 10% of triethanolamine, 6% to 8% of trisodium citrate, 3% to 6% of borax, 1% to 2% of organic phosphine compounds, 3% to 5% of methenamine, and the rest is water. The mixture is slightly heated to fully dissolve the substances in water, and stirred evenly to obtain the passion fruit shell extract compound liquid.
[0033] The organic phosphine compounds in the above-mentioned components include hydroxyethylidene diphosphonic acid, amino trimethylene phosphonic acid, ethylenediaminetetramethylene phosphonic acid, diethylenetriaminepentamethylene phosphonic acid, polyaminopolyether methylene phosphonic acid and hexamethylenediaminetetramethylene phosphonic acid and one or more of their potassium salts, sodium salts, ammonium salts and aluminum salts.
[0034] (V) Preparation of environmentally friendly organic metal corrosion inhibitors
[0035] The compound liquid of Macleaya oleifera pod extract (including the seeds in the pod) and passion fruit shell extract are compounded in a volume ratio of 5:1 to 1:1 to obtain an environmentally friendly organic metal corrosion inhibitor.
[0036] Application examples:
[0037] Application of the environmentally friendly organic metal corrosion inhibitor of the present application in the slow-release protection of metal aluminum in acidic and alkaline environments:
[0038] Example 1:
[0039] The passion fruit shell was washed with tap water, placed in a blast drying oven at 40°C and dried for 24 hours for later use. The passion fruit shell was crushed with a crusher, the crushed passion fruit shell material had a particle size of 120 μm, 10 g of the crushed passion fruit shell powder was put into a beaker, and 250 mL of 1 mol / L H 2 SO 4 The mixture was treated at 80° C. for 8 h, and after the reaction, a passion fruit shell extract a was obtained. The obtained passion fruit shell extract a was filtered, and the filtrate was concentrated to obtain a passion fruit shell extract b.
[0040] 20 g of passion fruit shell extract a, 3 g of passion fruit shell extract b, 8 g of triethanolamine, 7 g of trisodium citrate, 4 g of borax, 1 g of hydroxyethylidene diphosphonic acid, and 3 g of tropine are respectively added to 54 g of water, slightly heated to fully dissolve these substances in the water, and stirred evenly to obtain a passion fruit shell extract compound solution.
[0041] The fruit pods of Macleaya oleifera were rinsed with tap water, dried in a forced air drying oven at 40°C for 24 hours, and then used. The fruit pods of Macleaya oleifera were crushed with a grinder to a particle size of 100 μm, 5 g of the crushed fruit pod powder of Macleaya oleifera was put into a 500 mL reaction bottle, an extract of 125 mL of methanol and 125 mL of hydrochloric acid was added, ultrasonic extraction was performed at 60°C for 2 hours, and the filtrate was filtered and concentrated to obtain the Macleaya oleifera fruit pod extract.
[0042] The mixed solution of Macleaya oleifera pod extract and passion fruit shell extract was compounded in a volume ratio of 5:1 to obtain an environmentally friendly organic metal corrosion inhibitor.
[0043] When in use, first polish the aluminum standard metal specimen with a length of 4 cm, a width of 4 cm, and a thickness of 4 mm with sandpaper, clean it, then put it into 50 mL of acetone and 50 mL of anhydrous ethanol in turn and wipe it with absorbent cotton, take it out and place it on a clean filter paper, dry it with filter paper, place it in a vacuum drying oven at 40 ° C for 2 hours, take it out and put it in a dryer for use. Pour 20 mL of 1 mol / L HCL or 1 mol / L NaOH into two containers (container A and container B) respectively, container A is the blank control group experiment, and container B is the test group experiment. Then add 2 mL of the above-mentioned environmentally friendly organic metal corrosion inhibitor to container B, mix the corrosion inhibitor with 20 mL of 1 mol / L HCL or 1 mol / L NaOH, and then put the weighed aluminum sheet m into container A and container B respectively. A,0 and m B,0 , put container A and container B in a constant temperature 30℃ water bath for 12h. Then take out the aluminum sheet, rinse it with distilled water, soak it in anhydrous ethanol for about 3min, take it out and place it on a clean filter paper, dry it with the filter paper, put it in a vacuum drying oven at 40℃ for 2h, and weigh it on an analytical balance to obtain the mass of the aluminum sheet m A and m B , The metal release rate calculated under acidic conditions in this embodiment is 96.3%, and the metal release rate calculated under alkaline conditions is 95.6%.
[0044] Example 2:
[0045] The passion fruit shell was washed with tap water, placed in a blast drying oven at 40°C and dried for 24 hours for later use. The passion fruit shell was crushed with a crusher, the crushed passion fruit shell material had a particle size of 140 μm, 10 g of the crushed passion fruit shell powder was put into a beaker, and 300 mL of 1 mol / L H 2 SO 4The mixture was treated at 85° C. for 10 h, and after the reaction, a passion fruit shell extract a was obtained. The obtained passion fruit shell extract a was filtered, and the filtrate was concentrated to obtain a passion fruit shell extract b.
[0046] 25 g of passion fruit shell extract a, 4 g of passion fruit shell extract b, 9 g of triethanolamine, 8 g of trisodium citrate, 5 g of borax, 2 g of ethylenediaminetetramethylenephosphonic acid, and 4 g of tropine are respectively added to 43 g of water, slightly heated to fully dissolve these substances in the water, and stirred evenly to obtain a passion fruit shell extract compound solution.
[0047] The fruit pods of Macleaya oleifera were rinsed with tap water, dried in a forced air drying oven at 40°C for 24 hours, and then used. The fruit pods of Macleaya oleifera were crushed with a grinder to a particle size of 120 μm, 5 g of the crushed fruit pod powder of Macleaya oleifera was put into a 500 mL reaction bottle, an extract of 150 mL of methanol and 150 mL of hydrochloric acid was added, and ultrasonic extraction was performed at 80°C for 3 hours, filtered without washing, and the filtrate was concentrated to obtain the Macleaya oleifera fruit pod extract.
[0048] The mixed solution of Macleaya oleifera pod extract and passion fruit shell extract was compounded in a volume ratio of 3:1 to obtain an environmentally friendly organic metal corrosion inhibitor.
[0049] When in use, first polish the aluminum standard metal specimen with a length of 4 cm, a width of 4 cm, and a thickness of 4 mm with sandpaper, clean it, then put it into 50 mL of acetone and 50 mL of anhydrous ethanol in turn and wipe it with absorbent cotton, take it out and place it on a clean filter paper, dry it with filter paper, place it in a vacuum drying oven at 40 ° C for 2 hours, take it out and put it in a dryer for use. Pour 20 mL of 1 mol / L HCL or 1 mol / L NaOH into two containers (container A and container B) respectively, container A is the blank control group experiment, and container B is the test group experiment. Then add 4 mL of the above-mentioned environmentally friendly organic metal corrosion inhibitor to container B, mix the corrosion inhibitor with 20 mL of 1 mol / L HCL or 1 mol / L NaOH, and then put the weighed aluminum sheet m into container A and container B respectively. A,0 and m B,0 , put container A and container B in a constant temperature 40℃ water bath for 8h. Then take out the aluminum sheet, rinse it with distilled water, soak it in anhydrous ethanol for about 3min, take it out and place it on a clean filter paper, dry it with the filter paper, put it in a vacuum drying oven at 40℃ for 2h, and weigh it on an analytical balance to obtain the mass of the aluminum sheet m A and m B , The metal sustained-release rate calculated under acidic conditions in this implementation case is 97.2%, and the metal sustained-release rate calculated under alkaline conditions is 96.8%.
Claims
1. An environmentally friendly organic metal corrosion inhibitor suitable for all environments, characterized by: The method comprises the following steps: (1) preparing a passion fruit shell extract a; (2) filtering the extract a and concentrating the filtrate to obtain a passion fruit shell extract b; (3) preparing an extract of Macleaya oleifera pods (including the seeds in the pods); (4) preparing a mixed solution of the passion fruit shell extract; and (5) preparing an environmentally friendly organic metal corrosion inhibitor: the Macleaya oleifera pods (including the seeds in the pods) extract and the mixed solution of the passion fruit shell extract are mixed at a volume ratio of 5:1 to 1:1 to obtain an environmentally friendly organic metal corrosion inhibitor.
2. The environmentally friendly organic metal corrosion inhibitor suitable for all environments according to claim 1, characterized in that: The preparation of passion fruit shell extract a in the step (1) includes: (a) washing and drying passion fruit shell materials; (b) crushing passion fruit shell materials; (c) reacting passion fruit shell powder and 1 mol / L H2SO4 at a solid-to-liquid ratio (g / mL) of 1:25 to 1:35, with a mechanical stirring speed of 90 to 150 rpm and a reaction time of 8 to 10 hours, and obtaining passion fruit shell extract a after the reaction is completed.
3. The environmentally friendly organic metal corrosion inhibitor suitable for all environments according to claim 1, characterized in that: The preparation of the extract of Macleaya hupensis pods (including the seeds in the pods) in step (3) includes: (a) washing and drying the Macleaya hupensis pods; (b) crushing the Macleaya hupensis pods; (c) performing an extraction reaction of the Macleaya hupensis pods: adding the Macleaya hupensis pod powder to V 甲醇 :V 1％盐酸 =1:1 extract, solid-liquid ratio of 1:30-1:60 (g / mL), ultrasonic extraction at 60-80°C for 2-4 hours, filtration, and concentration of the filtrate to obtain the Macleaya cordata pod extract.
4. The environmentally friendly organic metal corrosion inhibitor suitable for all environments according to claim 1, characterized in that: The preparation of the passion fruit shell extract compound liquid in the step (4) comprises the following components in mass percentage: 20% to 25% of passion fruit shell extract a, 2% to 4% of passion fruit shell extract b, 8% to 10% of triethanolamine, 6% to 8% of trisodium citrate, 3% to 6% of borax, 1% to 2% of organic phosphine compounds, 3% to 5% of methenamine, and the rest is water. The mixture is slightly heated, fully dissolved in water, and stirred evenly to obtain the passion fruit shell extract compound liquid.