Composite corrosion inhibitor and preparation method thereof

Abstract

The invention discloses a composite corrosion inhibitor and a preparation method thereof, and relates to the technical field of corrosion inhibitors. Comprising the following components in parts by weight: 3 to 6 parts of amphoteric organic ionic salt, 5 to 8 parts of diazo alkyl urea, 1 to 3 parts of meso-tetramethyl-meso-tetra-p-aminophenyl calix [4] pyrrole, 3 to 5 parts of quinoline yellow, 2 to 4 parts of hydroxypropyl beta-cyclodextrin, 3 to 6 parts of N-[(4-methyl-1H-benzotriazole-1-yl) methyl] diethanolamine and 8 to 12 parts of triethanolamine borate. 1-3 parts of sodium benzotriazolyl butyl phenolsulfonate and 1-3 parts of inorganic salt. The composite corrosion inhibitor is high in corrosion inhibition efficiency, remarkable in effect, good in high temperature resistance, safe and environmentally friendly to use, and a good corrosion inhibition effect can be achieved by adding a small amount of the composite corrosion inhibitor.

Description

Technical Field

[0001] The present invention relates to the technical field of corrosion inhibitors, in particular to a composite corrosion inhibitor and a preparation method thereof. Background Art

[0002] Metals are among the most important and widely used materials in industry, finding widespread application in numerous fields, including transportation, bridges, vehicles, machinery, chemicals, and urban construction. Metals can undergo corrosion reactions during use, altering their properties and potentially affecting the safe operation of equipment. Slowing and inhibiting corrosion reactions in metals is crucial for protecting metal equipment and pipelines, and the use of corrosion inhibitors is an effective and readily achievable method.

[0003] Corrosion inhibitors are chemical substances that, when added to a corrosion inhibition system at a certain concentration, significantly reduce the corrosion rate of metals, with minimal effect on the concentration of the corrosive agent. Corrosion inhibitors are used in very small quantities. While they cannot alter the metal's tendency to corrode in a medium, they can form a protective film on the metal surface, slowing the corrosion rate and ultimately inhibiting corrosion. Compared to other corrosion prevention methods, corrosion inhibitors are convenient and cost-effective, making them widely used in industrial production and society. A wide variety of corrosion inhibitors are currently available on the market, each with its own unique performance and application range. Single corrosion inhibitors often suffer from drawbacks such as high dosage and limited effectiveness. This has led to the emergence of composite corrosion inhibitors, which have garnered widespread attention within the industry, offering hope for reducing inhibitor dosage while significantly improving inhibition efficiency. However, these composite corrosion inhibitors still suffer from technical drawbacks such as insufficient environmental performance, limited corrosion inhibition effectiveness and efficiency, high dosage requirements, and poor high-temperature resistance.

[0004] To address the above issues, Chinese invention patent publication CN103305851B discloses a supramolecular composite corrosion inhibitor and its preparation method for reducing corrosion of metal equipment during natural gas transportation. This method improves the corrosion inhibition efficiency of the corrosion inhibitor during natural gas transportation and reduces the amount of corrosion inhibitor used. The technical solution is as follows: the composite corrosion inhibitor is composed of a surfactant and a supramolecular polymer. The surfactant is sodium dodecylbenzenesulfonate, and the supramolecular polymer is acrylamide with cyclodextrin pendant groups. The mass ratio of the two monomers is 1:1. The preparation method involves first preparing the two monomers into a 100 mg / L sodium dodecylbenzenesulfonate solution and a 100 mg / L acrylamide with cyclodextrin pendant groups solution, respectively. Then, 100 mL of each solution is poured into a reaction flask. The reaction is carried out at a temperature of 25-40°C and a reaction time of 12-24 hours under constant stirring to produce the supramolecular composite corrosion inhibitor. This composite corrosion inhibitor is simple to prepare, requires mild conditions, and exhibits excellent synergistic corrosion inhibition. It is suitable for use in natural gas transportation. However, the corrosion inhibition efficiency and effect of the composite corrosion inhibitor still need to be further improved, and the high temperature resistance still needs to be further improved.

[0005] It can be seen that the development of a composite corrosion inhibitor with high corrosion inhibition efficiency, significant effect, good high temperature resistance, and better corrosion inhibition effect can be achieved by adding a small amount, and the use of a safe and environmentally friendly composite corrosion inhibitor and its preparation method meets market demand, has broad market value and application prospects, and is of great significance to promoting the development of the corrosion inhibitor field. Summary of the Invention

[0006] The purpose of the present invention is to overcome the shortcomings of the existing technology and provide a composite corrosion inhibitor with high corrosion inhibition efficiency, significant effect, good high temperature resistance, better corrosion inhibition effect can be achieved by adding a small amount, and safe and environmentally friendly use and its preparation method.

[0007] To achieve the above-mentioned purpose, the technical solution adopted by the present invention is: a composite corrosion inhibitor, comprising the following components in parts by weight: 3-6 parts of amphoteric organic ion salt, 5-8 parts of diazolidinyl urea, 1-3 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 3-5 parts of quinoline yellow, 2-4 parts of hydroxypropyl β-cyclodextrin, 3-6 parts of N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine, 8-12 parts of triethanolamine borate, 1-3 parts of sodium benzotriazolyl butylphenol sulfonate, and 1-3 parts of inorganic salt.

[0008] Preferably, the amphoteric organic ion salt is at least one of hydroxypropane sulfonic acid pyridinium salt, 1-benzylpyridine-3-carboxylate, and glycerolphosphorylcholine.

[0009] Preferably, there is no special requirement for the source of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole. In one embodiment of the present invention, the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical Reagents, 2002 (6): 344-345.

[0010] Preferably, the inorganic salt is at least one of borate, silicate and zinc salt.

[0011] Preferably, the borate is at least one of sodium borate and potassium borate; the silicate is sodium silicate; and the zinc salt is at least one of zinc nitrate and zinc sulfate.

[0012] Preferably, the composite corrosion inhibitor further comprises the following components: 3-5 parts of a hyperbranched sulfonate surfactant and 1-3 parts of sodium lignin sulfonate.

[0013] Preferably, there is no special requirement for the source of the hyperbranched sulfonate surfactant. In one embodiment of the present invention, the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0014] Preferably, the composite corrosion inhibitor comprises the following components in parts by weight: 3-5 parts of amphoteric organic ion salt, 6-7 parts of diazolidinyl urea, 1.5-2.5 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 3-5 parts of quinoline yellow, 2.5-3.5 parts of hydroxypropyl β-cyclodextrin, 5 parts of N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine, 9-10 parts of triethanolamine borate, 1 part of sodium benzotriazolyl butylphenol sulfonate, and 2 parts of inorganic salt.

[0015] Another object of the present invention is to provide a method for preparing the composite corrosion inhibitor, comprising the following steps: uniformly mixing the components by weight, grinding the mixture through a 300-600 mesh sieve, and obtaining the composite corrosion inhibitor.

[0016] Due to the application of the above technical solution, the present invention has the following beneficial effects:

[0017] (1) The preparation method of the composite corrosion inhibitor disclosed in the present invention only requires mixing the components evenly and then grinding them to the required mesh size. The process is simple, easy to operate, does not require special equipment, requires little capital investment, consumes little energy, has high preparation efficiency and finished product qualification rate, and is suitable for continuous large-scale production.

[0018] (2) The composite corrosion inhibitor disclosed in the present invention comprises the following components in parts by weight: 3-6 parts of amphoteric organic ion salt, 5-8 parts of diazolidinyl urea, 1-3 parts of meso-tetramethyl-meso-tetra-aminophenyl cup [4] pyrrole, 3-5 parts of quinoline yellow, 2-4 parts of hydroxypropyl β-cyclodextrin, 3-6 parts of N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine, 8-12 parts of triethanolamine borate, 1-3 parts of sodium benzotriazolyl butylphenol sulfonate, and 1-3 parts of inorganic salt. Through the mutual coordination and joint action of the components, the product has high corrosion inhibition efficiency, significant effect, good high temperature resistance, and can achieve good corrosion inhibition effect by adding a small amount. It is safe and environmentally friendly to use.

[0019] (3) The composite corrosion inhibitor disclosed in the present invention also includes the following components: 3-5 parts of a hyperbranched sulfonate surfactant and 1-3 parts of sodium lignin sulfonate. Through the interaction between the above components and other components, the compatibility between the components can be improved, the solubility can be improved, and the dispersion uniformity can be increased, so that the corrosion inhibitor prepared has better corrosion inhibition performance and better high temperature resistance. Through the rational selection of component formula, the corrosion inhibitor does not contain hexavalent chromate and heavy metal elements, has the advantages of being non-toxic and pollution-free, and is more green, safe and environmentally friendly to use. DETAILED DESCRIPTION

[0020] The following description is intended to disclose the present invention so that those skilled in the art can implement the present invention. The preferred embodiments described below are merely examples, and those skilled in the art may conceive of other obvious variations.

[0021] Example 1

[0022] A composite corrosion inhibitor comprises the following components in parts by weight: 3 parts of amphoteric organic ion salt, 5 parts of diazolidinyl urea, 1 part of meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 3 parts of quinoline yellow, 2 parts of hydroxypropyl β-cyclodextrin, 3 parts of N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine, 8 parts of triethanolamine borate, 1 part of sodium benzotriazolyl butylphenol sulfonate, and 1 part of inorganic salt.

[0023] The amphoteric organic ion salt is hydroxypropanesulfonic acid pyridinium salt; the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the inorganic salt is borate; the borate is sodium borate.

[0024] The composite corrosion inhibitor further comprises the following components: 3 parts of a hyperbranched sulfonate surfactant and 1 part of sodium lignin sulfonate; the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0025] A preparation method of the composite corrosion inhibitor comprises the following steps: uniformly mixing the components according to weight, grinding and passing through a 300-mesh sieve to obtain the composite corrosion inhibitor.

[0026] Example 2

[0027] A composite corrosion inhibitor comprises the following components in parts by weight: 4 parts of amphoteric organic ion salt, 6 parts of diazolidinyl urea, 1.5 parts of meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 3.5 parts of quinoline yellow, 2.5 parts of hydroxypropyl β-cyclodextrin, 4 parts of N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine, 9 parts of triethanolamine borate, 1.5 parts of sodium benzotriazolyl butylphenol sulfonate, and 1.5 parts of inorganic salt.

[0028] The amphoteric organic ion salt is 1-benzylpyridine-3-carboxylate; the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole can be found in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345; the inorganic salt is a silicate; the silicate is sodium silicate.

[0029] The composite corrosion inhibitor further comprises the following components: 3.5 parts of a hyperbranched sulfonate surfactant and 1.5 parts of sodium lignin sulfonate; the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0030] A preparation method of the composite corrosion inhibitor comprises the following steps: uniformly mixing the components according to weight, grinding and passing through a 400-mesh sieve to obtain the composite corrosion inhibitor.

[0031] Example 3

[0032] A composite corrosion inhibitor comprises the following components in parts by weight: 4.5 parts of amphoteric organic ion salt, 6.5 parts of diazolidinyl urea, 2 parts of meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 4 parts of quinoline yellow, 3 parts of hydroxypropyl β-cyclodextrin, 4.5 parts of N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine, 10 parts of triethanolamine borate, 2 parts of sodium benzotriazolyl butylphenol sulfonate, and 2 parts of inorganic salt.

[0033] The amphoteric organic ion salt is glycerophosphorylcholine; the preparation method of the meso-tetramethyl-meso-tetra-p-aminophenyl cup[4]pyrrole can be found in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup[4]pyrrole [J]. Chemical Reagents, 2002(6):344-345; the inorganic salt is a zinc salt; the zinc salt is zinc nitrate.

[0034] The composite corrosion inhibitor further comprises the following components: 4 parts of a hyperbranched sulfonate surfactant and 2 parts of sodium lignin sulfonate; the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0035] A preparation method of the composite corrosion inhibitor comprises the following steps: uniformly mixing the components according to weight, grinding and passing through a 450-mesh sieve to obtain the composite corrosion inhibitor.

[0036] Example 4

[0037] A composite corrosion inhibitor comprises the following components in parts by weight: 5 parts of amphoteric organic ion salt, 7 parts of diazolidinyl urea, 2.5 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup[4]pyrrole, 4.5 parts of quinoline yellow, 3.5 parts of hydroxypropyl β-cyclodextrin, 5 parts of N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine, 11 parts of triethanolamine borate, 2.5 parts of sodium benzotriazolyl butylphenol sulfonate, and 2.5 parts of inorganic salt.

[0038] The amphoteric organic ion salt is a mixture of hydroxypropanesulfonic acid pyridinium salt, 1-benzylpyridine-3-carboxylate, and glycerophosphorylcholine in a mass ratio of 1:2:3; the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, see: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the inorganic salt is a mixture of borate, silicate, and zinc salt in a mass ratio of 1:2:2; the borate is a mixture of sodium borate and potassium borate in a mass ratio of 3:5; the silicate is sodium silicate; the zinc salt is a mixture of zinc nitrate and zinc sulfate in a mass ratio of 1:3.

[0039] The composite corrosion inhibitor further comprises the following components: 4.5 parts of a hyperbranched sulfonate surfactant and 2.5 parts of sodium lignin sulfonate; the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0040] A preparation method of the composite corrosion inhibitor comprises the following steps: uniformly mixing the components according to weight, grinding and passing through a 550-mesh sieve to obtain the composite corrosion inhibitor.

[0041] Example 5

[0042] A composite corrosion inhibitor comprises the following components in parts by weight: 6 parts of amphoteric organic ion salt, 8 parts of diazolidinyl urea, 3 parts of meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, 5 parts of quinoline yellow, 4 parts of hydroxypropyl β-cyclodextrin, 6 parts of N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine, 12 parts of triethanolamine borate, 3 parts of sodium benzotriazolyl butylphenol sulfonate, and 3 parts of inorganic salt.

[0043] The amphoteric organic ion salt is hydroxypropanesulfonic acid pyridinium salt; the preparation method of the Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole is described in: Guo Yong, Shao Shijun, He Lijun, et al. Synthesis and Characterization of Meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole [J]. Chemical Reagents, 2002 (6): 344-345; the inorganic salt is borate; the borate is sodium borate.

[0044] The composite corrosion inhibitor further comprises the following components: 5 parts of a hyperbranched sulfonate surfactant and 3 parts of sodium lignin sulfonate; the hyperbranched sulfonate surfactant is prepared according to the preparation method of the hyperbranched sulfonate surfactant SHBP-1 in Example 1 of the Chinese invention patent with authorization announcement number CN102690641B.

[0045] A preparation method of the composite corrosion inhibitor comprises the following steps: uniformly mixing the components according to weight, grinding and passing through a 600-mesh sieve to obtain the composite corrosion inhibitor.

[0046] Comparative Example 1

[0047] A composite corrosion inhibitor and a preparation method thereof are substantially the same as those in Example 1, except that meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole and quinoline yellow are not added.

[0048] Comparative Example 2

[0049] A composite corrosion inhibitor and a preparation method thereof are substantially the same as those in Example 1, except that hydroxypropyl β-cyclodextrin and N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine are not added.

[0050] To further illustrate the beneficial technical effects of the composite corrosion inhibitors involved in each embodiment of the present invention, relevant performance tests were conducted on the composite corrosion inhibitors involved in Examples 1-5 and Comparative Examples 1-2. The test results are shown in Table 1. The test method is as follows: The corrosion inhibition rate test method (gravimetric method) commonly used in the industry was used for evaluation; 30mm×20mm×0.4mm A20 carbon steel test pieces were cleaned, dried, and weighed. They were then suspended in a corrosive medium of a 5wt% sodium chloride solution at 90°C and 160°C for 72 hours, respectively. The samples were then removed, cleaned, dried, and weighed. 20mg / L of each corrosion inhibitor from each embodiment was added to the corrosive medium. The weight loss of the test pieces under the same conditions was measured to calculate the corrosion inhibition rate of the corrosion inhibitor. The results are expressed as mass percentage.

[0051] Table 1

[0052] Test items 90℃ corrosion inhibition rate (%) 160℃ corrosion inhibition rate (%) Example 1 99.52 99.38 Example 2 99.68 99.60 Example 3 99.80 99.76 Example 4 99.91 99.89 Example 5 99.95 99.95 Comparative Example 1 98.84 97.98 Comparative Example 2 98.67 97.24

[0053] As can be seen from the data in Table 1, the composite corrosion inhibitors involved in the embodiments of the present invention have better corrosion inhibition effect and high temperature resistance than the comparative products; the combined use of meso-tetramethyl-meso-tetra-p-aminophenylcalix[4]pyrrole, quinoline yellow, hydroxypropyl β-cyclodextrin and N-[(4-methyl-1H-benzotriazol-1-yl)methyl]diethanolamine is beneficial to improving the above properties.

[0054] The above embodiments are only for illustrating the technical concept and features of the present invention. Their purpose is to enable people familiar with this technology to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of protection of the present invention.

Claims

1. A composite corrosion inhibitor, characterized in that: The invention comprises the following components in parts by weight: 3-6 parts of amphoteric organic ion salt, 5-8 parts of diazolidinyl urea, 1-3 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 3-5 parts of quinoline yellow, 2-4 parts of hydroxypropyl β-cyclodextrin, 3-6 parts of N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine, 8-12 parts of triethanolamine borate, 1-3 parts of sodium benzotriazolyl butylphenol sulfonate and 1-3 parts of inorganic salt.

2. The composite corrosion inhibitor according to claim 1, characterized in that The amphoteric organic ion salt is at least one of hydroxypropane sulfonate pyridinium salt, 1-benzylpyridine-3-carboxylate, and glycerolphosphorylcholine.

3. The composite corrosion inhibitor according to claim 1, characterized in that The inorganic salt is at least one of borates, silicates and zinc salts.

4. The composite corrosion inhibitor according to claim 3, characterized in that: The borate is at least one of sodium borate and potassium borate; the silicate is sodium silicate; and the zinc salt is at least one of zinc nitrate and zinc sulfate.

5. The composite corrosion inhibitor according to claim 1, characterized in that: The composite corrosion inhibitor further comprises the following components: 3-5 parts of hyperbranched sulfonate surfactant and 1-3 parts of sodium lignin sulfonate.

6. The composite corrosion inhibitor according to claim 1, characterized in that: The composite corrosion inhibitor comprises the following components in parts by weight: 3-5 parts of amphoteric organic ion salt, 6-7 parts of diazolidinyl urea, 1.5-2.5 parts of meso-tetramethyl-meso-tetra-p-aminophenyl cup [4] pyrrole, 3-5 parts of quinoline yellow, 2.5-3.5 parts of hydroxypropyl β-cyclodextrin, 5 parts of N-[(4-methyl-1H-benzotriazole-1-yl)methyl]diethanolamine, 9-10 parts of triethanolamine borate, 1 part of sodium benzotriazolyl butylphenol sulfonate, and 2 parts of inorganic salt.

7. A method for preparing the composite corrosion inhibitor according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: uniformly mixing the components according to weight proportions, grinding and passing through a 300-600 mesh sieve to obtain a composite corrosion inhibitor.