CN112458464B - High-molecular carbon steel corrosion inhibitor and preparation method thereof - Google Patents
High-molecular carbon steel corrosion inhibitor and preparation method thereof Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
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Abstract
The invention discloses a novel polymer carbon steel corrosion inhibitor and a preparation method thereof, wherein the polymer carbon steel corrosion inhibitor consists of a structural unit provided by amino acid, a structural unit provided by a primary amine compound of C2-C10, a structural unit provided by a carboxylic acid compound of C2-C10 and a structural unit provided by an organic sulfide, and comprises the following raw materials in parts by weight: 15-30 parts of amino acid, 10-45 parts of primary amine compound, 20-35 parts of carboxylic acid compound, 20-30 parts of organic sulfide and 150-200 parts of water. The novel polymer carbon steel corrosion inhibitor disclosed by the invention can form a stable and firm protective film on the surface of metal, can effectively prevent the metal from being corroded, has excellent corrosion inhibition performance, and has corrosion inhibition performance superior to that of a phosphorus carbon steel corrosion inhibitor. The novel polymer phosphorus-free carbon steel corrosion inhibitor contains a large number of amino acid groups, is easy to biodegrade, belongs to green water treatment chemicals, and cannot cause secondary pollution to a system and even the environment in the using process.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a novel high-molecular carbon steel corrosion inhibitor and a preparation method thereof.
Background
At present, the varieties of water treatment chemicals in China are not complete, most of the varieties are analyzed, imitated or developed according to foreign patents, and the phenomena of weak foundation, backward technology and low overall level are caused by the short industrial development and limited scientific research funding of the water treatment chemicals in China. The difference between the variety and foreign countries is mainly reflected in the water treatment chemicals of the novel environment-friendly water-soluble copolymer.
At present, carbon steel corrosion inhibitors still mainly adopt phosphorus and zinc salt formulas. Phosphorus-containing compounds in phosphorus water treatment chemicals account for a considerable proportion, such as inorganic phosphates, organic phosphoric acids, phosphine carboxylic acids and the like, and are still absolutely dominant so far because of the wide application of excellent cost performance in industrial circulating cooling systems.
In recent years, although many achievements are made on the formulas of low-phosphorus and phosphorus-free water treatment agents at home and abroad, for example, CN111003822A, CN109133387A, CN102351327B and CN104150617B report on phosphorus-free scale and corrosion inhibitors, the corrosion inhibition performance still cannot meet the requirement of practical application, and inorganic corrosion inhibitors such as zinc salt, molybdate and the like are required to be compounded to improve the performance of the corrosion inhibitor. The zinc salt, molybdate and other compound products have short timeliness, are unstable, have higher requirements on the alkalinity and other environmental conditions, are easy to separate out and cause secondary pollution easily.
With the increasing requirement of environmental protection, phosphorus and refractory water treatment chemicals are bound to be limited, and are replaced by novel green water treatment agents and environment-friendly 'pollutant zero emission technology'.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a novel polymer carbon steel corrosion inhibitor and a preparation method thereof, and aims to solve the problems that the prior art has secondary environmental pollution and poor corrosion inhibition effect, and a phosphorus-free carbon steel corrosion inhibitor cannot completely replace a phosphorus-containing medicament and a zinc salt compound medicament.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a novel high-molecular carbon steel corrosion inhibitor comprises a structural unit provided by amino acid, a structural unit provided by a primary amine compound of C2-C10, a structural unit provided by a carboxylic acid compound of C2-C10 and a structural unit provided by organic sulfide.
As further optimization, the high-molecular carbon steel corrosion inhibitor comprises the following raw materials in parts by weight: 15-30 parts of amino acid, 10-45 parts of primary amine compound, 20-35 parts of carboxylic acid compound, 20-30 parts of organic sulfide and 150-200 parts of water.
As a further optimization, the amino acid is one or more of L-aspartic acid, N-lauroyl sarcosine, glutamic acid and phenylalanine.
As a further optimization, the organic sulfide is one or two of thiourea and S-carboxyethyl thiosuccinic acid.
As a further optimization, the carboxylic acid compound is one or more of adipic acid, succinic acid, maleic acid and oxalic acid.
As a further optimization, the primary amine compound is one or more of hexamethylene diamine, p-phenylene diamine, ethylene diamine and propane diamine.
In order to solve the technical problems, the invention provides a preparation method of a novel polymer carbon steel corrosion inhibitor, which comprises the following steps:
s1: dissolving 15-30 parts by weight of amino acid, 10-45 parts by weight of primary amine compound and 20-35 parts by weight of carboxylic acid compound in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 140-165 ℃ for 1-2 hours;
s2: preparation of organic sulfide solution: dissolving 20-30 parts by weight of organic sulfide in 50-100 parts by weight of water, and uniformly mixing;
s3: slowly dripping the organic sulfide solution of S2 into the solution of S1 at the temperature of 150-160 ℃ for 1-3 h;
s4: after the dropwise addition, heating and refluxing for 1-2h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the target product.
In order to solve the technical problems, the invention provides a preparation method of a novel polymer carbon steel corrosion inhibitor, which comprises the following steps:
s1: dissolving 15-30 parts by weight of amino acid and 20-35 parts by weight of carboxylic acid compound in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 140-165 ℃ for 1-2 h;
s2: dissolving 20-30 parts by weight of organic sulfide and 10-45 parts by weight of primary amine compound in 50-100 parts by weight of water, and uniformly mixing;
s3: slowly dripping the mixed solution of S2 into the solution of S1 at the temperature of 150-160 ℃ for 1-3 h;
s4: after the dropwise addition, heating and refluxing for 1-2h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the target product.
A new-type high-molecular multi-component corrosion inhibitor for carbon steel is prepared from the multi-polar high-molecular multi-component copolymer prepared from amino acid, primary amino compound, carboxylic acid compound and organosulfide through the step-by-step condensation reaction, and features that its molecular chain contains a lot of multi-polar functional groups (amide group, amino acid group, mercapto group and carboxylic acid), the element containing lone pair of electrons (N, O, S), unsaturated chemical bond, polar functional group and empty track (d track) on metal surface form hybridized coordinate bond. The protective film can block the formation of corrosion cells and prevent corrosion ions from reaching the metal surface.
The invention has the beneficial effects that:
1) the novel polymer carbon steel corrosion inhibitor forms a stable and firm protective film on the surface of metal, can effectively prevent the metal corrosion, has excellent corrosion inhibition performance, and has corrosion inhibition performance superior to that of a phosphorus carbon steel corrosion inhibitor.
2) The novel phosphorus-free high molecular corrosion inhibitor has stable and firm film formation, wide application range and low requirement on the quality of circulating water, and can achieve good effect under various water qualities.
3) The protective film formed by the novel polymer phosphorus-free carbon steel corrosion inhibitor is not interfered by corrosive ions and is suitable for a cooling circulating water system with high chloride ions and high concentration multiple.
4) The novel polymer phosphorus-free carbon steel corrosion inhibitor contains a large number of amino acid groups, is easy to biodegrade, belongs to green water treatment chemicals, and cannot cause secondary pollution to a system and even the environment in the using process.
Detailed Description
The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples.
Example 1
S1: dissolving 15 parts by weight of glutamic acid, 45 parts by weight of p-phenylenediamine and 35 parts by weight of maleic acid in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 150 ℃ for 2 hours;
s2: preparation of organic sulfide solution: dissolving 30 parts by weight of S-carboxyethyl thiosuccinic acid in 100 parts by weight of water, and uniformly mixing;
s3: slowly dropwise adding the S-carboxyethyl thiosuccinic acid solution of S2 into the solution of S1 under the stirring state, wherein the dropwise adding temperature is 155 +/-5 ℃, and the dropwise adding time is controlled to be 3 hours;
s4: after the dropwise addition, heating and refluxing for 2h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor.
Example 2
S1: dissolving 20 parts by weight of L-aspartic acid, 30 parts by weight of hexamethylenediamine and 30 parts by weight of adipic acid in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 165 ℃ for 1.5 hours;
s2: preparation of organic sulfide solution: dissolving 25 parts by weight of thiourea in 75 parts by weight of water, and mixing uniformly;
s3: slowly dripping the thiourea solution of S2 into the solution of S1 under the stirring state, wherein the dripping temperature is 150 +/-5 ℃, and the dripping time is controlled to be 2 h;
s4: after the dropwise addition, heating and refluxing for 1.5h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor.
Example 3
S1: dissolving 30 parts by weight of phenylalanine, 10 parts by weight of ethylenediamine and 20 parts by weight of oxalic acid in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 140 ℃ for 1 h;
s2: preparation of organic sulfide solution: dissolving 20 parts by weight of thiourea in 50 parts by weight of water, and mixing uniformly;
s3: slowly dripping the thiourea solution of S2 into the solution of S1 under the stirring state, wherein the dripping temperature is 155 +/-5 ℃, and the dripping time is controlled to be 1 h;
s4: after the dropwise addition, heating and refluxing for 1h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor.
Example 4
S1: dissolving 10 parts by weight of L-aspartic acid, 10 parts by weight of N-lauroyl sarcosine and 30 parts by weight of maleic acid in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 165 ℃ for 1 h;
s2: dissolving 25 parts by weight of thiourea and 25 parts by weight of ethylenediamine in 75 parts by weight of water, and uniformly mixing;
s3: slowly dripping the mixed solution of S2 into the solution of S1 under the stirring state, wherein the dripping temperature is 155 +/-5 ℃, and the dripping time is controlled to be 2 hours;
s4: after the dropwise addition, heating and refluxing for 1.5h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor.
Example 5
S1: dissolving 15 parts by weight of glutamic acid and 20 parts by weight of oxalic acid in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 150 ℃ for 1 h;
s2: dissolving 20 parts by weight of S-carboxyethyl thiosuccinic acid and 45 parts by weight of hexamethylenediamine in 100 parts by weight of water, and uniformly mixing;
s3: slowly dripping the mixed solution of S2 into the solution of S1 under the stirring state, wherein the dripping temperature is 155 +/-5 ℃, and the dripping time is controlled to be 1 h;
s4: after the dropwise addition, heating and refluxing for 1h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor.
Comparative example 1
The preparation method of the polymer carbon steel corrosion inhibitor is the same as that of the preparation method of the embodiment 2, except that adipic acid in S1 is replaced by formic acid, and the addition amount of the adipic acid is unchanged.
Comparative example 2
The preparation method of the high molecular carbon steel corrosion inhibitor is the same as that of the preparation method of the example 2, except that hexamethylenediamine is replaced by methylamine in S1, and the addition amount of the methylamine is unchanged.
Comparative example 3
The preparation method of the polymer carbon steel corrosion inhibitor is the same as the preparation method of the embodiment 2, and the difference is that the dripping temperature in the S3 is controlled to be 110 +/-5 ℃.
Comparative example 4
The preparation method of the polymer carbon steel corrosion inhibitor is the same as the preparation method of the embodiment 2, except that the reaction temperature in the S4 is controlled at 110 +/-5 ℃.
The corrosion inhibitors prepared in the examples and comparative examples were tested for corrosion inhibition performance, as well as for hydroxyethylidene diphosphonic acid (HEDP), aminotrimethylene phosphonic Acid (ATMP), polyamino polyether methylene phosphonic acid (papamp), 2-phosphonic butane-1, 2, 4-tricarboxylic acid (PBTC) and its zinc sulfate compound corrosion inhibitor, as well as polyepoxysuccinic acid, polyaspartic acid. The corrosion inhibition performance is tested under different dosing concentrations (5 mg/L, 10mg/L and 15 mg/L). A water sample is taken from circulating cooling water (chloride ions: 1817mg/L, sulfate radicals: 1036mg/L, hardness: 876mg/L, alkalinity: 574mg/L and concentration ratio: 11.5 times) of a power plant, a corrosion inhibition performance test method is carried out according to the GB/T18175-2014 rotary hanging piece method, a hanging piece material is 20# carbon steel, and a table 1 shows a corrosion inhibition efficiency (unit%) test result under different dosing concentrations.
TABLE 1 Corrosion inhibition efficiency test results at different dosing concentrations
| Concentration of the drug | 5mg/L | 10mg/L | 15mg/L |
| Example 1 | 72.3 | 90.6 | 94.1 |
| Example 2 | 74.2 | 91.4 | 95.5 |
| Example 3 | 73.4 | 91.2 | 94.7 |
| Example 4 | 71.1 | 87.9 | 93.9 |
| Example 5 | 73.9 | 90.3 | 95.0 |
| Comparative example 1 | 68.8 | 84.3 | 89.1 |
| Comparative example 2 | 67.4 | 82.9 | 88.5 |
| Comparative example 3 | 69.1 | 85.7 | 90.4 |
| Comparative example 4 | 66.8 | 80.5 | 85.6 |
| PBTC | 53.7 | 58.7 | 72.7 |
| PAPEMP | 57.3 | 65.3 | 78.5 |
| ATMP | 51.6 | 56.9 | 71.8 |
| HEDP + Zinc salt | 68.9 | 81.9 | 86.2 |
| PBTC + zinc salt | 65.7 | 75.6 | 80.3 |
| PAPEMP + zinc salt | 69.1 | 82.4 | 87.7 |
| ATMP + zinc salt | 63.6 | 71.6 | 85.9 |
| Polyaspartic acid | 55.4 | 62.4 | 72.6 |
| Polyepoxysuccinic acid | 56.1 | 63.2 | 75.1 |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention; those skilled in the art can make various changes, modifications and alterations without departing from the scope of the invention, and all equivalent changes, modifications and alterations to the disclosed technology are equivalent embodiments of the present invention; meanwhile, any changes, modifications, and evolutions of the equivalent changes of the above embodiments according to the actual techniques of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (1)
1. A macromolecule carbon steel corrosion inhibitor is characterized in that the macromolecule carbon steel corrosion inhibitor is composed of a structural unit provided by amino acid, a structural unit provided by primary amine compound of C2-C10, a structural unit provided by carboxylic acid compound of C2-C10 and a structural unit provided by organic sulfide;
the high-molecular carbon steel corrosion inhibitor comprises the following raw materials in parts by weight: 15-30 parts by weight of amino acid, 10-45 parts by weight of primary amine compound, 20-35 parts by weight of carboxylic acid compound, 20-30 parts by weight of organic sulfide, and 150-200 parts by weight of water;
the preparation method of the polymer carbon steel corrosion inhibitor comprises the following steps:
s1: dissolving 15-30 parts by weight of amino acid, 10-45 parts by weight of primary amine compound and 20-35 parts by weight of carboxylic acid compound in 100 parts by weight of water, uniformly mixing, and keeping the temperature at 140-165 ℃ for 1-2 hours;
s2: preparation of organic sulfide solution: dissolving 20-30 parts by weight of organic sulfide in 50-100 parts by weight of water, and uniformly mixing;
s3: slowly dripping the organic sulfide solution of S2 into the solution of S1 at the temperature of 150-160 ℃ for 1-3 h;
s4: after the dropwise addition, heating and refluxing for 1-2h to obtain colorless to light yellow transparent liquid, and cooling to room temperature to obtain the high-molecular carbon steel corrosion inhibitor;
the amino acid is one or more of L-aspartic acid, N-lauroyl sarcosine, glutamic acid and phenylalanine;
the organic sulfide is one or two of thiourea and S-carboxyethyl thiosuccinic acid;
the carboxylic acid compound is one or more of adipic acid, succinic acid, maleic acid and oxalic acid;
the primary amine compound is one or more of hexamethylene diamine, p-phenylenediamine, ethylenediamine and propane diamine.
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